Organosilica materials and uses thereof

ABSTRACT

Methods of preparing organosilica materials, which are a polymer comprising of at least one independent cyclic polyurea monomer of Formula 
     
       
         
         
             
             
         
       
     
     wherein each R 1  is a Z 1 OZ 2 Z 3 SiZ 4  group, wherein each Z 1  represents a hydrogen atom, a C 1 -C 4  alkyl group, or a bond to a silicon atom of another monomer unit; each Z 2  and Z 3  independently represent a hydroxyl group, a C 1 -C 4  alkyl group, a C 1 -C 4  alkoxy group or an oxygen atom bonded to a silicon atom of another monomer unit; and each Z 4  represents a C 1 -C 8  alkylene group bonded to a nitrogen atom of the cyclic polyurea are provided herein. Methods of preparing and processes of using the organosilica materials, e.g., for gas separation, color removal, etc., are also provided herein.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of provisional U.S. Ser. No.62/091,071 and provisional U.S. Ser. No. 62/091,077, filed Dec. 12,2014, the entire contents of which are expressly incorporated byreference herein.

This application is also related to several other co-pending U.S.applications, filed on even date herewith and bearing Attorney DocketNos. 2014EM304-US2 (entitled “Organosilica Materials and Uses Thereof”),2014EM305-US2 (entitled “Methods of Producing Organosilica Materials andUses Thereof”), 2015EM382 (entitled “Aromatic Hydrogenation Catalystsand Uses Thereof”), 2015EM383 (entitled “Organosilica Materials and UsesThereof”), 2015EM384 (entitled “Organosilica Materials and UsesThereof”), 2015EM385 (entitled “Organosilica Materials and UsesThereof”), 2015EM387 (entitled “Coating Method Using OrganosilicaMaterials and Uses Thereof”), 2015EM388 (entitled “Membrane FabricationMethod Using Organosilica Materials and Uses Thereof”), 2015EM389(entitled “Adsorbent for Heteroatom Species Removal and Uses Thereof”),and 2015EM390 (entitled “Method for Separating Aromatic Compounds fromLube Basestocks”), the entire disclosures of each of which areincorporated by reference herein.

Additionally, this application is further related to several otherco-pending U.S. applications, filed on even date herewith and bearingAttorney Docket Nos. 2015EM375 (entitled “Organosilica Materials for Useas Adsorbents for Oxygenate Removal”), 2015EM376 (entitled “SupportedCatalyst for Olefin Polymerization”), 2015EM377 (entitled “SupportedCatalyst for Olefin Polymerization”), 2015EM378 (entitled “SupportedCatalyst for Olefin Polymerization”), and 2015EM379 (entitled “SupportedCatalyst for Olefin Polymerization”), the entire disclosures of each ofwhich are incorporated by reference herein.

FIELD OF THE INVENTION

The present invention relates to organosilica materials, methods ofmaking and uses thereof.

BACKGROUND OF THE INVENTION

Porous inorganic solids have found great utility as catalysts andseparation media for industrial application. In particular, mesoporousmaterials, such as silicas and aluminas, having a periodic arrangementof mesopores are attractive materials for use in adsorption, separationand catalysis processes due to their uniform and tunable pores, highsurface areas and large pore volumes. The pore structure of suchmesoporous materials is large enough to absorb large molecules and thepore wall structure can be as thin as about 1 nm. Further, suchmesoporous materials are known to have large specific surface areas(e.g., 1000 m²/g) and large pore volumes (e.g., 1 cm³/g). For thesereasons, such mesoporous materials enable reactive catalysts, adsorbentscomposed of a functional organic compound, and other molecules torapidly diffuse into the pores and therefore, can be advantageous overzeolites, which have smaller pore sizes. Consequently, such mesoporousmaterials can be useful not only for catalysis of high-speed catalyticreactions, but also as large capacity adsorbents.

It was further discovered that the inclusion of some organic groups inthe mesoporous framework can provide adjustable reactive surfaces andalso contributes to uniformity in pore size, higher mechanical strength,and hydrothermal stability of the material. Thus, mesoporousorganosilica materials can exhibit unique properties compared tomesoporous silica such as enhanced hydrothermal stability, chemicalstability, and mechanical properties. Organic groups can be incorporatedusing bridged silsesquioxane precursors of the form Si—R—Si to formmesoporous organosilicas.

Mesoporous organosilicas are conventionally formed by the self-assemblyof the silsequioxane precursor in the presence of a structure directingagent, a porogen and/or a framework element. The precursor ishydrolysable and condenses around the structure directing agent. Thesematerials have been referred to as Periodic Mesoporous Organosilicates(PMOs), due to the presence of periodic arrays of parallel alignedmesoscale channels. For example, Landskron, K., et al. [Science,302:266-269 (2003)] report the self-assembly of1,3,5-tris[diethoxysila]cylcohexane [(EtO)₂SiCH₂]₃ in the presence of abase and the structure directing agent, cetyltrimethylammonium bromideto form PMOs that are bridged organosilicas with a periodic mesoporousframework, which consist of SiO₃R or SiO₂R₂ building blocks, where R isa bridging organic group. In PMOs, the organic groups can behomogenously distributed in the pore walls. U.S. Pat. Pub. No.2012/0059181 reports the preparation of a crystalline hybridorganic-inorganic silicate formed from 1,1,3,3,5,5 hexaethoxy-1,3,5trisilyl cyclohexane in the presence of NaAlO₂ and base. U.S. PatentApplication Publication No. 2007/003492 reports preparation of acomposition formed from 1,1,3,3,5,5 hexaethoxy-1,3,5 trisilylcyclohexane in the presence of propylene glycol monomethyl ether.

However, the use of a structure directing agent, such as a surfactant,in the preparation of an organosilica material, such as a PMO, requiresa complicated, energy intensive process to eliminate the structuredirecting agent at the end of the preparation process. This limits theability to scale-up the process for industrial applications. Therefore,there is a need to provide additional organosilica materials with adesirable pore diameter, pore volume and surface area. Further, there isa need to provide such organosilica materials that can be prepared by amethod that can be practiced in the absence of a structure directingagent, a porogen or surfactant.

SUMMARY OF THE INVENTION

It has been found that an organosilica material with desirable porediameter, pore volume, and surface area can be achieved. Further, suchorganosilica material can be successfully prepared without the need fora structure directing agent, a porogen or surfactant.

Thus, in one aspect, embodiments of the invention provide anorganosilica material, which is a polymer of at least one independentcyclic polyurea monomer of Formula

wherein each R¹ independently is a Z¹OZ²Z³SiZ⁴ group, wherein each Z¹represents a hydrogen atom, a C₁-C₄ alkyl group, or a bond to a siliconatom of another monomer unit; each Z² and Z³ independently represent ahydroxyl group, a C₁-C₄ alkyl group, a C₁-C₄ alkoxy group or an oxygenatom bonded to a silicon atom of another monomer unit; and each Z⁴represents a C₁-C₈ alkylene group bonded to a nitrogen atom of thecyclic polyurea; and optionally at least one other monomer selected fromthe group consisting of: (i) an independent unit of Formula[Z⁵OZ⁶SiCH₂]₃ (II), wherein each Z⁵ represents a hydrogen atom, a C₁-C₄alkyl or a bond to a silicon atom of another monomer, and each Z⁶represents a hydroxyl group, a C₁-C₄ alkyl group, a C₁-C₄ alkoxy group,or an oxygen atom bonded to a silicon atom of another monomer; (ii) anindependent unit of Formula Z⁷OZ⁸Z⁹Z¹⁰Si (III), wherein each Z⁷represents a hydrogen atom, a C₁-C₄ alkyl group or a bond to a siliconatom of another monomer; and Z⁸, Z⁹ and Z¹⁰ are each independentlyselected from the group consisting of a hydroxyl group, a C₁-C₄ alkylgroup, a C₁-C₄ alkoxy group, a nitrogen-containing C₁-C₁₀ alkyl group, anitrogen-containing heteroaralkyl group, and a nitrogen-containingoptionally substituted heterocycloalkyl group, and an oxygen atom bondedto a silicon atom of another monomer; and (iii) an independent unit ofFormula Z¹¹Z¹²Z¹³Si—R²-SiZ¹¹Z¹²Z¹³(IV), wherein each Z¹¹ independentlyrepresents a hydroxyl group, a C₁-C₄ alkoxy group or an oxygen bonded toa silicon atom of another comonomer; each Z¹² and Z¹³ independentlyrepresent a hydroxyl group, a C₁-C₄ alkoxy group, a C₁-C₄ alkyl group oran oxygen bonded to a silicon atom of another monomer; and each R² aC₁-C₈ alkylene group, a C₂-C₈ alkenylene group, a C₂-C₈ alkynylenegroup, a nitrogen-containing C₂-C₁₀ alkylene group, an optionallysubstituted C₆-C₂₀ aralkyl and an optionally substituted C₄-C₂₀heterocycloalkyl group; (iv) an independent unit of Formula M¹(OZ¹⁴)₃(V), wherein M¹ represents a Group 13 metal and each Z¹⁴ independentlyrepresents a hydrogen atom, a C₁-C₆ alkyl or a bond to a silicon atom ofanother monomer; (v) an independent unit of Formula(Z¹⁵O)₂M²-O—Si(OZ¹⁶)₃ (VI), wherein M² represents a Group 13 metal andeach Z¹⁵ and each Z¹⁶ independently represent a hydrogen atom, a C₁-C₆alkyl group or a bond to a silicon atom of another monomer; and (vi) acombination thereof.

In still another aspect, embodiments of the invention provide a methodfor preparing the organosilica material described herein, the methodcomprising: (a) providing an aqueous mixture that contains essentiallyno structure directing agent and/or porogen, (b) adding at least onecyclic compound of Formula

into the aqueous mixture to form a solution, wherein each R³ isindependently a X¹OX²X³SiX⁴ group, wherein each X¹ represents a C₁-C₄alkyl group; each X² and X³ independently represent a C₁-C₄ alkyl group,or a C₁-C₄ alkoxy group; and each X⁴ represents a C₁-C₈ alkylene groupbonded to a nitrogen atom of the cyclic compound; (c) aging the solutionto produce a gel; and (d) drying the gel to obtain an organosilicamaterial which is a polymer comprising independent polyurea units ofFormula (I).

In still another aspect, embodiments of the invention provide a methodfor reducing impurities in a liquid hydrocarbon product comprisingcontacting the liquid hydrocarbon product with the organosilica materialdescribed herein.

In still another aspect, embodiments of the invention provide a methodimproving color in a diesel fuel product comprising contacting thediesel fuel product with the organosilica material described hereinresulting in an improved color diesel fuel product.

Other embodiments, including particular aspects of the embodimentssummarized above, will be evident from the detailed description thatfollows.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates a UV-Vis adsorption spectra for diesel feed treatedwith Sample 3 and diesel feed.

FIG. 2 illustrates color improvement of a diesel feed treated withSample 3.

FIG. 3 illustrates an XRD spectrum for Sample 1.

FIG. 4 illustrates an XRD spectrum for Sample 2.

DETAILED DESCRIPTION OF THE INVENTION

In various aspects of the invention, organosilica materials, methods forpreparing organosilica materials and gas and liquid separation processesusing the organosilica materials are provided.

I. Definitions

For purposes of this invention and the claims hereto, the numberingscheme for the Periodic Table Groups is according to the IUPAC PeriodicTable of Elements.

The term “and/or” as used in a phrase such as “A and/or B” herein isintended to include “A and B”, “A or B”, “A”, and “B”.

The terms “substituent”, “radical”, “group”, and “moiety” may be usedinterchangeably.

As used herein, and unless otherwise specified, the term “C_(n)” meanshydrocarbon(s) having n carbon atom(s) per molecule, wherein n is apositive integer.

As used herein, and unless otherwise specified, the term “hydrocarbon”means a class of compounds containing hydrogen bound to carbon, andencompasses (i) saturated hydrocarbon compounds, (ii) unsaturatedhydrocarbon compounds, and (iii) mixtures of hydrocarbon compounds(saturated and/or unsaturated), including mixtures of hydrocarboncompounds having different values of n.

As used herein, and unless otherwise specified, the term “alkyl” refersto a saturated hydrocarbon radical having from 1 to 12 carbon atoms(i.e. C₁-C₁₂ alkyl), particularly from 1 to 8 carbon atoms (i.e. C₁-C₈alkyl), particularly from 1 to 6 carbon atoms (i.e. C₁-C₆ alkyl), andparticularly from 1 to 4 carbon atoms (i.e. C₁-C₄ alkyl). Examples ofalkyl groups include, but are not limited to, methyl, ethyl, propyl,butyl, pentyl, hexyl, heptyl, octyl, decyl, and so forth. The alkylgroup may be linear, branched or cyclic. “Alkyl” is intended to embraceall structural isomeric forms of an alkyl group. For example, as usedherein, propyl encompasses both n-propyl and isopropyl; butylencompasses n-butyl, sec-butyl, isobutyl and tert-butyl and so forth. Asused herein, “C₁ alkyl” refers to methyl (—CH₃), “C₂ alkyl” refers toethyl (—CH₂CH₃), “C₃ alkyl” refers to propyl (—CH₂CH₂CH₃) and “C₄ alkyl”refers to butyl (e.g. —CH₂CH₂CH₂CH₃,—(CH₃)CHCH₂CH₃, —CH₂CH(CH₃)₂, etc.).Further, as used herein, “Me” refers to methyl, and “Et” refers toethyl, “i-Pr” refers to isopropyl, “t-Bu” refers to tert-butyl, and “Np”refers to neopentyl.

As used herein, and unless otherwise specified, the term “alkylene”refers to a divalent alkyl moiety containing 1 to 12 carbon atoms (i.e.C₁-C₁₂ alkylene) in length and meaning the alkylene moiety is attachedto the rest of the molecule at both ends of the alkyl unit. For example,alkylenes include, but are not limited to, —CH₂—, —CH₂CH₂—,—CH(CH₃)CH₂—, —CH₂CH₂CH₂—, etc. The alkylene group may be linear orbranched.

As used herein, and unless otherwise specified, the term“nitrogen-containing alkyl” refers to an alkyl group as defined hereinwherein one or more carbon atoms in the alkyl group is substituted witha nitrogen atom or a nitrogen-containing cyclic hydrocarbon having from2 to 10 carbon atoms (i.e., a nitrogen-containing cyclic C₂-C₁₀hydrocarbon), particularly having from 2 to 5 carbon atoms (i.e., anitrogen-containing cyclic C₂-C₅ hydrocarbon), and particularly havingfrom 2 to 5 carbon atoms (i.e., a nitrogen-containing cyclic C₂-C₅hydrocarbon). The nitrogen-containing cyclic hydrocarbon may have one ormore nitrogen atoms. The nitrogen atom(s) may optionally be substitutedwith one or two C₁-C₆ alkyl groups. The nitrogen-containing alkyl canhave from 1 to 12 carbon atoms (i. e. C₁-C₁₂ nitrogen-containing alkyl),particularly from 1 to 10 carbon atoms (i.e. C₁-C₁₀ nitrogen-containingalkyl), particularly from 2 to 10 carbon atoms (i.e. C₂-C₁₀nitrogen-containing alkyl), particularly from 3 to 10 carbon atoms (i.e.C₃-C₁₀ nitrogen-containing alkyl), and particularly from 3 to 8 carbonatoms (i.e. C₁-C₁₀ nitrogen-containing alkyl). Examples ofnitrogen-containing alkyls include, but are not limited to,

As used herein, and unless otherwise specified, the term“nitrogen-containing alkylene” refers to an alkylene group as definedherein wherein one or more carbon atoms in the alkyl group issubstituted with a nitrogen atom. The nitrogen atom(s) may optionally besubstituted with one or two C₁-C₆ alkyl groups. The nitrogen-containingalkylene can have from 1 to 12 carbon atoms (i. e. C₁-C₁₂nitrogen-containing alkylene), particularly from 2 to 10 carbon atoms(i.e. C₂-C₁₀ nitrogen-containing alkylene), particularly from 3 to 10carbon atoms (i.e. C₃-C₁₀ nitrogen-containing alkylene), particularlyfrom 4 to 10 carbon atoms (i.e. C₄-C₁₀ nitrogen-containing alkylene),and particularly from 3 to 8 carbon atoms (i.e. C₃-C₈nitrogen-containing alkyl). Examples of nitrogen-containing alkylenesinclude, but are not limited to,

As used herein, and unless otherwise specified, the term “alkenyl”refers to an unsaturated hydrocarbon radical having from 2 to 12 carbonatoms (i.e., C₂-C₁₂ alkenyl), particularly from 2 to 8 carbon atoms(i.e., C₂-C₈ alkenyl), particularly from 2 to 6 carbon atoms (i.e.,C₂-C₆ alkenyl), and having one or more (e.g., 2, 3, etc.) carbon-carbondouble bonds. The alkenyl group may be linear, branched or cyclic.Examples of alkenyls include, but are not limited to ethenyl (vinyl),2-propenyl, 3-propenyl, 1,4-pentadienyl, 1,4-butadienyl, 1-butenyl,2-butenyl and 3-butenyl. “Alkenyl” is intended to embrace all structuralisomeric forms of an alkenyl. For example, butenyl encompasses1,4-butadienyl, 1-butenyl, 2-butenyl and 3-butenyl, etc.

As used herein, and unless otherwise specified, the term “alkenylene”refers to a divalent alkenyl moiety containing 2 to about 12 carbonatoms (i.e. C₂-C₁₂ alkenylene) in length and meaning that the alkylenemoiety is attached to the rest of the molecule at both ends of the alkylunit. For example, alkenylenes include, but are not limited to,—CH═CH—,—CH═CHCH₂—, —CH═CH═CH—, —CH₂CH₂CH═CHCH₂—, etc. —CH₂CH₂—,—CH(CH₃)CH₂—, —CH₂CH₂CH₂—, etc. The alkenylene group may be linear orbranched.

As used herein, and unless otherwise specified, the term “alkynyl”refers to an unsaturated hydrocarbon radical having from 2 to 12 carbonatoms (i.e., C₂-C₁₂ alkynyl), particularly from 2 to 8 carbon atoms(i.e., C₂-C₈ alkynyl), particularly from 2 to 6 carbon atoms (i.e.,C₂-C₆ alkynyl), and having one or more (e.g., 2, 3, etc.) carbon-carbontriple bonds. The alkynyl group may be linear, branched or cyclic.Examples of alkynyls include, but are not limited to ethynyl,1-propynyl, 2-butynyl, and 1,3-butadiynyl. “Alkynyl” is intended toembrace all structural isomeric forms of an alkynyl. For example,butynyl encompassses 2-butynyl, and 1,3-butadiynyl and propynylencompasses 1-propynyl and 2-propynyl (propargyl).

As used herein, and unless otherwise specified, the term “alkynylene”refers to a divalent alkynyl moiety containing 2 to about 12 carbonatoms (i.e. C₂-C₁₂ alkenylene) in length and meaning that the alkylenemoiety is attached to the rest of the molecule at both ends of the alkylunit. For example, alkenylenes include, but are not limited to,—C≡C—,—C≡CCH₂—, —C≡CCH₂C≡C—,—CH₂CH₂C≡CCH₂—, etc. —CH₂CH₂—, —CH(CH₃)CH₂—,—CH₂CH₂CH₂—, etc. The alkynlene group may be linear or branched.

As used herein, and unless otherwise specified, the term “alkoxy” refersto —O-alkyl containing from 1 to about 10 carbon atoms. The alkoxy maybe straight-chain or branched-chain. Non-limiting examples includemethoxy, ethoxy, propoxy, butoxy, isobutoxy, tert-butoxy, pentoxy, andhexoxy. “C₁ alkoxy” refers to methoxy, “C₂ alkoxy” refers to ethoxy, “C₃alkoxy” refers to propoxy and “C₄ alkoxy” refers to butoxy. Further, asused herein, “OMe” refers to methoxy and “OEt” refers to ethoxy.

As used herein, and unless otherwise specified, the term “aromatic”refers to unsaturated cyclic hydrocarbons having a delocalizedconjugated π system and having from 5 to 20 carbon atoms (aromaticC₅-C₂₀ hydrocarbon), particularly from 5 to 12 carbon atoms (aromaticC₅-C₁₂ hydrocarbon), and particularly from 5 to 10 carbon atoms(aromatic C₅-C₁₂ hydrocarbon). Exemplary aromatics include, but are notlimited to benzene, toluene, xylenes, mesitylene, ethylbenzenes, cumene,naphthalene, methylnaphthalene, dimethylnaphthalenes, ethylnaphthalenes,acenaphthalene, anthracene, phenanthrene, tetraphene, naphthacene,benzanthracenes, fluoranthrene, pyrene, chrysene, triphenylene, and thelike, and combinations thereof. Additionally, the aromatic may compriseone or more heteroatoms. Examples of heteroatoms include, but are notlimited to, nitrogen, oxygen, and/or sulfur. Aromatics with one or moreheteroatom include, but are not limited to furan, benzofuran, thiophene,benzothiophene, oxazole, thiazole and the like, and combinationsthereof. The aromatic may comprise monocyclic, bicyclic, tricyclic,and/or polycyclic rings (in some embodiments, at least monocyclic rings,only monocyclic and bicyclic rings, or only monocyclic rings) and may befused rings.

As used herein, and unless otherwise specified, the term “aryl” refersto any monocyclic or polycyclic cyclized carbon radical containing 6 to14 carbon ring atoms, wherein at least one ring is an aromatichydrocarbon. Examples of aryls include, but are not limited to phenyl,naphthyl, pyridinyl, and indolyl.

As used herein, and unless otherwise specified, the term “aralkyl”refers to an alkyl group substituted with an aryl group. The alkyl groupmay be a C₁-C₁₀ alkyl group, particularly a C₁-C₆, particularly a C₁-C₄alkyl group, and particularly a C₁-C₃ alkyl group. Examples of aralkylgroups include, but are not limited to phenymethyl, phenylethyl, andnaphthylmethyl. The aralkyl may comprise one or more heteroatoms and bereferred to as a “heteroaralkyl.” Examples of heteroatoms include, butare not limited to, nitrogen (i.e., nitrogen-containing heteroaralkyl),oxygen (i.e., oxygen-containing heteroaralkyl), and/or sulfur (i.e.,sulfur-containing heteroaralkyl). Examples of heteroaralkyl groupsinclude, but are not limited to, pyridinylethyl, indolylmethyl,furylethyl, and quinolinylpropyl.

As used herein, and unless otherwise specified, the term “heterocyclo”refers to fully saturated, partially saturated or unsaturated orpolycyclic cyclized carbon radical containing from 4 to 20 carbon ringatoms and containing one or more heteroatoms atoms. Examples ofheteroatoms include, but are not limited to, nitrogen (i.e.,nitrogen-containing heterocyclo), oxygen (i.e., oxygen-containingheterocyclo), and/or sulfur (i.e., sulfur-containing heterocyclo).Examples of heterocyclo groups include, but are not limited to, thienyl,furyl, pyrrolyl, piperazinyl, pyridyl, benzoxazolyl, quinolinyl,imidazolyl, pyrrolidinyl, and piperidinyl.

As used herein, and unless otherwise specified, the term“heterocycloalkyl” refers to an alkyl group substituted with heterocyclogroup. The alkyl group may be a C₁-C₁₀ alkyl group, particularly aC₁-C₆, particularly a C₁-C₄ alkyl group, and particularly a C₁-C₃ alkylgroup. Examples of heterocycloalkyl groups include, but are not limitedto thienylmethyl, furylethyl, pyrrolylmethyl, piperazinylethyl,pyridylmethyl, benzoxazolylethyl, quinolinylpropyl, andimidazolylpropyl.

As used herein, the term “hydroxyl” refers to an —OH group.

As used herein, the term “mesoporous” refers to solid materials havingpores that have a diameter within the range of from about 2 nm to about50 nm.

As used herein, the term “organosilica” refers to an organosiloxanecompound that comprises one or more organic groups bound to two or moreSi atoms.

As used herein, the term “silanol” refers to a Si—OH group.

As used herein, the term “silanol content” refers to the percent of theSi—OH groups in a compound and can be calculated by standard methods,such as NMR.

As used herein, the terms “structure directing agent,” “SDA,” and/or“porogen” refer to one or more compounds added to the synthesis media toaid in and/or guide the polymerization and/or polycondensing and/ororganization of the building blocks that form the organosilica materialframework. Further, a “porogen” is understood to be a compound capableof forming voids or pores in the resultant organosilica materialframework. As used herein, the term “structure directing agent”encompasses and is synonymous and interchangeable with the terms“templating agent” and “template.”

As used herein, and unless otherwise specified, the term “adsorption”includes physisorption, chemisorption, and condensation onto a solidmaterial and combinations thereof.

II. Organosilica Materials

The invention relates to organosilica materials. In a first embodiment,the organosilica material may be a polymer of at least one independentcyclic polyurea monomer of Formula

wherein each R¹ independently can be a Z¹OZ²Z³SiZ⁴ group, wherein eachZ¹ can be a hydrogen atom, a C₁-C₄ alkyl group, or a bond to a siliconatom of another monomer unit; each Z² and Z³ independently can be ahydroxyl group, a C₁-C₄ alkyl group, a C₁-C₄ alkoxy group or an oxygenatom bonded to a silicon atom of another monomer unit; and each Z⁴ canbe a C₁-C₈ alkylene group bonded to a nitrogen atom of the cyclicpolyuria.

As used herein, and unless otherwise specified, “a bond to a siliconatom of another monomer” means the bond can advantageously displace amoiety (particularly an oxygen-containing moiety such as a hydroxyl, analkoxy or the like), if present, on a silicon atom of the anothermonomer so there may be a bond directly to the silicon atom of theanother monomer thereby connecting the two monomers, e.g., via a Si—O—Silinkage. As used herein, and unless otherwise specified, “an oxygen atombonded to a silicon atom of another monomer” means that the oxygen atomcan advantageously displace a moiety (particularly an oxygen-containingmoiety such as a hydroxyl, an alkoxy or the like), if present, on asilicon atom of the another monomer so the oxygen atom may be bondeddirectly to the silicon atom of the another monomer thereby connectingthe two monomers, e.g., via a Si—O—Si linkage. For clarity, in theaforementioned bonding scenarios, the “another monomer” can be a monomerof the same type or a monomer of a different type.

IIA. Monomers of Formula (I)

In various embodiments, each Z¹ can be a hydrogen atom.

Additionally or alternatively, each Z¹ can be a C₁-C₄ alkyl group, aC₁-C₃ alkyl group, a C₁-C₂ alkyl group or methyl.

Additionally or alternatively, each Z¹ can be a bond to a silicon atomof another siloxane monomer.

Additionally or alternatively, each Z¹ can be a hydrogen atom, a C₁-C₂alkyl group or a bond to a silicon atom of another monomer.

Additionally or alternatively, each Z² and Z³ independently can be ahydroxyl group.

Additionally or alternatively, each Z² and Z³ independently can be aC₁-C₄ alkyl group, a C₁-C₃ alkyl group, a C₁-C₂ alkyl group or methyl.

Additionally or alternatively, each Z² and Z³ independently can be aC₁-C₄ alkoxy group, a C₁-C₃ alkoxy group, a C₁-C₂ alkoxy group ormethoxy.

Additionally or alternatively, each Z² and Z³ independently can be anoxygen atom bonded to a silicon atom of another monomer unit.

Additionally or alternatively, each Z² and Z³ independently can be ahydroxyl group, a C₁-C₂ alkyl group, a C₁-C₂ alkoxy group, or an oxygenatom bonded to a silicon atom of another monomer unit.

Additionally or alternatively, each Z¹ can be a hydrogen atom, a C₁-C₂alkyl group or a bond to a silicon atom of another monomer; and each Z²and Z³ independently can be a hydroxyl group, a C₁-C₂ alkyl group, aC₁-C₂ alkoxy group, or an oxygen atom bonded to a silicon atom ofanother monomer unit.

Additionally or alternatively, each Z⁴ can be a C₁-C₇ alkylene groupbonded to a nitrogen atom of the cyclic polyurea, a C₁-C₇ alkylene groupbonded to a nitrogen atom of the cyclic polyurea, a C₁-C₆ alkylene groupbonded to a nitrogen atom of the cyclic polyurea, a C₁-C₄ alkylene groupbonded to a nitrogen atom of the cyclic polyurea, a C₁-C₃ alkylene groupbonded to a nitrogen atom of the cyclic polyurea, a C₁-C₂ alkylene groupbonded to a nitrogen atom of the cyclic polyurea, or —CH₂— bonded to anitrogen atom of the cyclic polyurea.

Additionally or alternatively, each Z¹ can be a hydrogen atom, a C₁-C₂alkyl group or a bond to a silicon atom of another monomer; each Z² andZ³ independently can be a hydroxyl group, a C₁-C₂ alkyl group, a C₁-C₂alkoxy group, or an oxygen atom bonded to a silicon atom of anothermonomer unit; and each Z⁴ can be a C₁-C₄ alkylene group bonded to anitrogen atom of the cyclic polyurea.

Additionally or alternatively, each Z¹ can be a hydrogen atom or a bondto a silicon atom of another monomer; each Z² and Z³ independently canbe a hydroxyl group, a C₁-C₂ alkyl group or an oxygen atom bonded to asilicon atom of another monomer unit; and each Z⁴ can be a C₁-C₄alkylene group bonded to a nitrogen atom of the cyclic polyurea.

Additionally or alternatively, each Z¹ can be a hydrogen atom or a bondto a silicon atom of another monomer; each Z² and Z³ independently canbe a hydroxyl group or an oxygen atom bonded to a silicon atom ofanother monomer unit; and each Z⁴ can be a C₁-C₄ alkylene group bondedto a nitrogen atom of the cyclic polyurea.

In a particular embodiment, each Z¹ can be a hydrogen atom, methyl, or abond to a silicon atom of another monomer; each Z² and Z³ independentlycan be a hydroxyl group, methoxy or an oxygen atom bonded to a siliconatom of another monomer unit; and each Z⁴ can be —CH₂CH₂CH₂— bonded to anitrogen atom of the cyclic polyurea.

In another particular embodiment, each Z¹ can be a hydrogen atom or abond to a silicon atom of another monomer; each Z² and Z³ independentlycan be a hydroxyl group or an oxygen atom bonded to a silicon atom ofanother monomer unit; and each Z⁴ can be —CH₂CH₂CH₂— bonded to anitrogen atom of the cyclic polyurea.

II.B. Monomers of Formula (II)

In various embodiments, the organosilica material may further compriseanother monomer in combination with independent units of Formula (I),such as at least one independent unit of Formula [Z⁵OZ⁶SiCH₂]₃ (II),wherein each Z⁵ can be a hydrogen atom, a C₁-C₄ alkyl group or a bond toa silicon atom of another monomer, and each Z⁶ can be a hydroxyl group,a C₁-C₄ alkyl group, a C₁-C₄ alkoxy group or an oxygen atom bonded to asilicon atom of another monomer.

In various embodiments, each Z⁵ can be a hydrogen atom.

Additionally or alternatively, each Z⁵ can be a C₁-C₄ alkyl group, aC₁-C₃ alkyl group, a C₁-C₂ alkyl group or methyl.

Additionally or alternatively, each Z⁵ can be a bond to a silicon atomof another monomer.

Additionally or alternatively, each Z⁵ can be a hydrogen atom, a C₁-C₂alkyl group or a bond to a silicon atom of another monomer.

Additionally or alternatively, each Z⁶ can be a hydroxyl group.

Additionally or alternatively, each Z⁶ can be a C₁-C₄ alkyl group, aC₁-C₃ alkyl group, a C₁-C₂ alkyl group or methyl.

Additionally or alternatively, each Z⁶ can be a C₁-C₄ alkoxy group, aC₁-C₃ alkoxy group, a C₁-C₂ alkoxy group or methoxy.

Additionally or alternatively, each Z⁶ can be an oxygen atom bonded to asilicon atom of another monomer.

Additionally or alternatively, each Z⁶ can be a hydroxyl group, a C₁-C₂alkyl group, a C₁-C₂ alkoxy group, or an oxygen atom bonded to a siliconatom of another monomer.

Additionally or alternatively, each Z⁵ can be a hydrogen atom, a C₁-C₂alkyl group or a bond to a silicon atom of another monomer and each Z⁶can be a hydroxyl group, a C₁-C₂ alkyl group, a C₁-C₂ alkoxy group, oran oxygen atom bonded to a silicon atom of another monomer.

Additionally or alternatively, each Z⁵ can be a hydrogen atom or a bondto a silicon atom of another monomer and each Z⁶ can be a hydroxylgroup, a C₁-C₂ alkyl group, or an oxygen atom bonded to a silicon atomof another monomer.

In a particular embodiment, each Z⁵ can be a hydrogen atom or a bond toa silicon atom of another monomer and each Z⁶ can be a hydroxyl group oran oxygen atom bonded to a silicon atom of another monomer.

In another embodiment, each Z⁵ can be a hydrogen atom, ethyl or a bondto a silicon atom of another monomer and each Z⁶ can be a hydroxylgroup, ethoxy, or an oxygen atom bonded to a silicon atom of anothermonomer.

In another embodiment, each Z⁵ can be a hydrogen atom, ethyl or a bondto a silicon atom of another monomer and each Z⁶ can be methyl.

II.C. Monomers of Formula (III)

In various embodiments, the organosilica material may further compriseanother monomer in combination with independent units of Formula (I),such as at least one independent unit of Formula Z⁷OZ⁸Z⁹Z¹⁰Si (III),wherein each Z⁷ represents a hydrogen atom, a C₁-C₄ alkyl group or abond to a silicon atom of another monomer; and Z⁸, Z⁹ and Z¹⁰ are eachindependently selected from the group consisting of a hydroxyl group, aC₁-C₄ alkyl group, a C₁-C₄ alkoxy group, a nitrogen-containing C₁-C₁₀alkyl group, a nitrogen-containing heteroaralkyl group, and anitrogen-containing optionally substituted heterocycloalkyl group, andan oxygen atom bonded to a silicon atom of another monomer; and

In various aspects, each Z⁷ can be a hydrogen atom.

Additionally or alternatively, each Z⁷ can be a C₁-C₄ alkyl group, aC₁-C₃ alkyl group, a C₁-C₂ alkyl group or methyl.

Additionally or alternatively, each Z⁷ can be a hydrogen atom or a C₁-C₂alkyl group.

Additionally or alternatively, each Z⁷ can be a bond to a silicon atomof another monomer.

Additionally or alternatively, each Z⁷ can be a hydrogen atom, a C₁-C₂alkyl group or a bond to a silicon atom of another monomer.

Additionally or alternatively, each Z⁷ can be a hydrogen atom, ethyl,methyl or a bond to a silicon atom of another monomer.

Additionally or alternatively, Z⁸, Z⁹ and Z¹⁰ each independently can bea hydroxyl group.

Additionally or alternatively, each Z⁷ can be a hydrogen atom, a C₁-C₂alkyl group or a bond to a silicon atom of another monomer; and Z⁸, Z⁹and Z¹⁰ each independently can be a hydroxyl group.

Additionally or alternatively, Z⁸, Z⁹ and Z¹⁰ each independently can bea C₁-C₄ alkyl group, a C₁-C₃ alkyl group, a C₁-C₂ alkyl group or methyl.

Additionally or alternatively, Z⁸, Z⁹ and Z¹⁰ each independently can bea hydroxyl group or a C₁-C₂ alkyl group.

Additionally or alternatively, each Z⁷ can be a hydrogen atom, a C₁-C₂alkyl group or a bond to a silicon atom of another monomer; and Z⁸, Z⁹and Z¹⁰ each independently can be a hydroxyl group or a C₁-C₂ alkylgroup.

Additionally or alternatively, Z⁸, Z⁹ and Z¹⁰ each independently can bea C₁-C₄ alkoxy group, a C₁-C₃ alkoxy group, a C₁-C₂ alkoxy group ormethoxy.

Additionally or alternatively, Z⁸, Z⁹ and Z¹⁰ each independently can beselected from the group consisting of a hydroxyl group, a C₁-C₂ alkylgroup and a C₁-C₂ alkoxy group.

Additionally or alternatively, each Z⁷ can be a hydrogen atom, a C₁-C₂alkyl group or a bond to a silicon atom of another monomer; and Z⁸, Z⁹and Z¹⁰ each can be selected from the group consisting of a hydroxylgroup, a C₁-C₂ alkyl group and a C₁-C₂ alkoxy group.

Additionally or alternatively, Z⁸, Z⁹ and Z¹⁰ each independently can bea nitrogen-containing C₁-C₁₀ alkyl group, a nitrogen-containing C₁-C₉alkyl group, a nitrogen-containing C₁-C₈ alkyl group, anitrogen-containing C₁-C₇ alkyl group, a nitrogen-containing C₁-C₆ alkylgroup, a nitrogen-containing C₁-C₅ alkyl group, a nitrogen-containingC₁-C₄ alkyl group, a nitrogen-containing C₁-C₃ alkyl group, anitrogen-containing C₁-C₂ alkyl group, or a methylamine. In particular,Z⁸, Z⁹ and Z¹⁰ each independently can be a nitrogen-containing C₂-C₁₀alkyl group, a nitrogen-containing C₃-C₁₀ alkyl group, anitrogen-containing C₃-C₉ alkyl group, or a nitrogen-containing C₃-C₈alkyl group. The aforementioned nitrogen-containing alkyl groups mayhave one or more nitrogen atoms (e.g., 2, 3, etc.). Examples ofnitrogen-containing containing C₁-C₁₀ alkyl groups include, but are notlimited to,

Additionally or alternatively, Z⁸, Z⁹ and Z¹⁰ each independently can beselected from the group consisting of a hydroxyl group, a C₁-C₂ alkylgroup, a C₁-C₂ alkoxy group and a nitrogen-containing C₃-C₁₀ alkylgroup.

Additionally or alternatively, each Z⁷ can be a hydrogen atom, a C₁-C₂alkyl group or a bond to a silicon atom of another monomer; and Z⁸, Z⁹and Z¹⁰ each independently can be selected from the group consisting ofa hydroxyl group, a C₁-C₂ alkyl group, a C₁-C₂ alkoxy group and anitrogen-containing C₃-C₁₀ alkyl group.

Additionally or alternatively, Z⁸, Z⁹ and Z¹⁰ each independently can bea nitrogen-containing heteroaralkyl group. The nitrogen-containingheteroaralkyl group can be a nitrogen-containing C₄-C₁₂ heteroaralkylgroup, a nitrogen-containing C₄-C₁₀ heteroaralkyl group, or anitrogen-containing C₄-C₈ heteroaralkyl group. Examples ofnitrogen-containing heteroaralkyl groups include but are not limited topyridinylethyl, pyridinylpropyl, pyridinylmethyl, indolylmethyl,pyrazinylethyl, and pyrazinylpropyl. The aforementionednitrogen-containing heteroaralkyl groups may have one or more nitrogenatoms (e.g., 2, 3, etc.).

Additionally or alternatively, Z⁸, Z⁹ and Z¹⁰ each independently can beselected from the group consisting of a hydroxyl group, a C₁-C₂ alkylgroup, a C₁-C₂ alkoxy group, nitrogen-containing C₃-C₁₀ alkyl group anda nitrogen-containing heteroaralkyl group.

Additionally or alternatively, each Z⁷ can be a hydrogen atom, a C₁-C₂alkyl group or a bond to a silicon atom of another monomer; and Z⁸, Z⁹and Z¹⁰ each independently can be selected from the group consisting ofa hydroxyl group, a C₁-C₂ alkyl group, a C₁-C₂ alkoxy group, anitrogen-containing C₃-C₁₀ alkyl group and a nitrogen-containingheteroaralkyl group.

Additionally or alternatively, Z⁸, Z⁹ and Z¹⁰ each independently can bea nitrogen-containing heterocycloalkyl group, wherein theheterocycloalkyl group may be optionally substituted with a C₁-C₆ alkylgroup, particularly a C₁-C₄ alkyl group. The nitrogen-containingheterocycloalkyl group can be a nitrogen-containing C₄-C₁₂heterocycloalkyl group, a nitrogen-containing C₄-C₁₀ heterocycloalkylgroup, or a nitrogen-containing C₄-C₈ heterocycloalkyl group. Examplesof nitrogen-containing heterocycloalkyl groups include but are notlimited to piperazinylethyl, piperazinylpropyl, piperidinylethyl,piperidinylpropyl. The aforementioned nitrogen-containingheterocycloalkyl groups may have one or more nitrogen atoms (e.g., 2, 3,etc.).

Additionally or alternatively, Z⁸, Z⁹ and Z¹⁰ each independently can beselected from the group consisting of a hydroxyl group, a C₁-C₂ alkylgroup, a C₁-C₂ alkoxy group, nitrogen-containing C₃-C₁₀ alkyl group, anitrogen-containing heteroaralkyl group, and a nitrogen-containingoptionally substituted heterocycloalkyl group.

Additionally or alternatively, each Z⁷ can be a hydrogen atom, a C₁-C₂alkyl group or a bond to a silicon atom of another monomer; and Z⁸, Z⁹and Z¹⁰ each independently can be selected from the group consisting ofa hydroxyl group, a C₁-C₂ alkyl group, a C₁-C₂ alkoxy group, anitrogen-containing C₃-C₁₀ alkyl group, a nitrogen-containingheteroaralkyl group and a nitrogen-containing optionally substitutedheterocycloalkyl group.

Additionally or alternatively, Z⁸, Z⁹ and Z¹⁰ each independently can bean oxygen atom bonded to a silicon atom of another monomer.

Additionally or alternatively, each Z⁷ can be a hydrogen atom, a C₁-C₂alkyl group or a bond to a silicon atom of another monomer; and Z⁸, Z⁹and Z¹⁰ each independently can be selected from the group consisting ofa hydroxyl group, a C₁-C₂ alkyl group, a C₁-C₂ alkoxy group, anitrogen-containing C₃-C₁₀ alkyl group, a nitrogen-containingheteroaralkyl group, a nitrogen-containing optionally substitutedheterocycloalkyl group and an oxygen atom bonded to a silicon atom ofanother monomer.

Additionally or alternatively, each Z⁷ can be a hydrogen atom, a C₁-C₂alkyl group or a bond to a silicon atom of another monomer; and Z⁸, Z⁹and Z¹⁰ each independently can be selected from the group consisting ofa hydroxyl group, a C₁-C₂ alkyl group, a C₁-C₂ alkoxy group, anitrogen-containing C₃-C₈ alkyl group, C₄-C₁₀ heteroaralkyl group, anitrogen-containing optionally substituted C₄-C₁₀ heterocycloalkylgroup, and an oxygen atom bonded to a silicon atom of another monomer.

Additionally or alternatively, each Z⁷ can be a hydrogen atom or a bondto a silicon atom of another monomer; and Z⁸, Z⁹ and Z¹⁰ eachindependently can be selected from the group consisting of a hydroxylgroup, a C₁-C₂ alkyl group, a nitrogen-containing C₃-C₁₀ alkyl group,C₄-C₁₀ heteroaralkyl group, a nitrogen-containing optionally substitutedC₄-C₁₀ heterocycloalkyl group, and an oxygen atom bonded to a siliconatom of another monomer.

Additionally or alternatively, each Z⁷ can be a hydrogen atom, methyl,ethyl, or a bond to a silicon atom of another comonomer; and Z⁸, Z⁹ andZ¹⁰ each independently can be selected from the group consisting of ahydroxyl group, methoxy, ethoxy, methyl,

and an oxygen bonded to a silicon atom of another monomer.

In a particular embodiment, each Z⁷ can be a hydrogen atom, ethyl or abond to a silicon atom of another monomer; and Z⁸, Z⁹ and Z¹⁰ eachindependently can be selected from the group consisting of a hydroxylgroup, ethoxy, and an oxygen atom bonded to a silicon atom of anothermonomer.

In another particular embodiment, each Z⁷ can be a hydrogen atom, ethylor a bond to a silicon atom of another comonomer; Z⁸ and Z⁹ eachindependently can be selected from the group consisting of a hydroxylgroup, ethoxy, and an oxygen atom bonded to a silicon atom of anothermonomer; and each Z¹⁰ can be methyl.

In another particular embodiment, each Z⁷ can be a hydrogen atom, methylor a bond to a silicon atom of another comonomer; Z⁸ and Z⁹ eachindependently can be selected from the group consisting of a hydroxylgroup, methoxy, and an oxygen atom bonded to a silicon atom of anothermonomer; and each Z¹⁰ can be

In another particular embodiment, each Z⁷ can be a hydrogen atom, ethylor a bond to a silicon atom of another comonomer; Z⁸ and Z⁹ eachindependently can be selected from the group consisting of a hydroxylgroup, ethoxy, and an oxygen atom bonded to a silicon atom of anothermonomer; and each Z¹⁰ can be

In another particular embodiment, each Z⁷ can be a hydrogen atom, ethylor a bond to a silicon atom of another comonomer; Z⁸ and Z⁹ eachindependently can be selected from the group consisting of a hydroxylgroup, ethoxy, and an oxygen atom bonded to a silicon atom of anothermonomer; and each Z¹⁰ can be

In another particular embodiment, each Z⁷ can be a hydrogen atom, ethylor a bond to a silicon atom of another comonomer; Z⁸ and Z⁹ eachindependently can be selected from the group consisting of a hydroxylgroup, ethoxy, and an oxygen atom bonded to a silicon atom of anothermonomer; and each Z¹⁰ can be

In another particular embodiment, each Z⁷ can be a hydrogen atom, ethylor a bond to a silicon atom of another comonomer; Z⁸ and Z⁹ eachindependently can be selected from the group consisting of a hydroxylgroup, ethoxy, and an oxygen atom bonded to a silicon atom of anothermonomer; and Z¹⁰ can be

In another particular embodiment, each Z⁷ can be a hydrogen atom, ethylor a bond to a silicon atom of another comonomer; Z⁸ and Z⁹ eachindependently can be selected from the group consisting of a hydroxylgroup, ethoxy, and an oxygen atom bonded to a silicon atom of anothermonomer; and each Z¹⁰ can be

II.D. Monomers of Formula (IV)

In various embodiments, the organosilica material may further compriseanother monomer in combination with independent units of Formula (I),such as at least one independent unit of FormulaZ¹¹Z¹²Z¹³Si—R²—SiZ¹¹Z¹²Z¹³ (IV), wherein each Z¹¹ independentlyrepresents a hydroxyl group, a C₁-C₄ alkoxy group or an oxygen bonded toa silicon atom of another comonomer; each Z¹² and Z¹³ independentlyrepresent a hydroxyl group, a C₁-C₄ alkoxy group, a C₁-C₄ alkyl group oran oxygen bonded to a silicon atom of another monomer; and each R² aC₁-C₈ alkylene group, a C₂-C₈ alkenylene group, a C₂-C₈ alkynylenegroup, a nitrogen-containing C₂-C₁₀ alkylene group, an optionallysubstituted C₆-C₂₀ aralkyl and an optionally substituted C₄-C₂₀heterocycloalkyl group.

In various aspects, each Z¹¹ can be a hydroxyl group.

Additionally or alternatively, each Z¹¹ can be a C₁-C₄ alkoxy group, aC₁-C₃ alkoxy group, a C₁-C₂ alkoxy group or methoxy.

Additionally or alternatively, each Z¹¹ can be a hydroxyl group or aC₁-C₂ alkoxy group.

Additionally or alternatively, each Z¹¹ can be an oxygen atom bonded toa silicon atom of another comonomer.

Additionally or alternatively, each Z¹¹ can be a hydroxyl group, a C₁-C₂alkoxy group or an oxygen atom bonded to a silicon atom of anothercomonomer.

Additionally or alternatively, each Z¹¹ can be a hydroxyl group or anoxygen atom bonded to a silicon atom of another comonomer.

Additionally or alternatively, each Z¹² and Z¹³ independently can be ahydroxyl group.

Additionally or alternatively, each Z¹² and Z¹³ independently can be aC₁-C₄ alkoxy group, a C₁-C₃ alkoxy group, a C₁-C₂ alkoxy group ormethoxy.

Additionally or alternatively, each Z¹² and Z¹³ independently can be ahydroxyl group or a C₁-C₂ alkoxy group.

Additionally or alternatively, each Z¹² and Z¹³ independently can be aC₁-C₄ alkyl group, a C₁-C₃ alkyl group, a C₁-C₂ alkyl group or methyl.

Additionally or alternatively, each Z¹² and Z¹³ independently can be ahydroxyl group, a C₁-C₂ alkoxy group, or a C₁-C₂ alkyl group.

Additionally or alternatively, each Z¹² and Z¹³ independently can be anoxygen atom bonded to a silicon atom of another comonomer.

Additionally or alternatively, each Z¹² and Z¹³ independently can be ahydroxyl group, a C₁-C₂ alkoxy group, a C₁-C₂ alkyl group, or an oxygenatom bonded to a silicon atom of another comonomer.

Additionally or alternatively, each Z¹² and Z¹³ independently can be ahydroxyl group, a C₁-C₂ alkyl group, or an oxygen atom bonded to asilicon atom of another comonomer.

Additionally or alternatively, each Z¹¹ can be a hydroxyl group, a C₁-C₂alkoxy group or an oxygen atom bonded to a silicon atom of anothercomonomer; and each Z¹² and Z¹³ independently can be a hydroxyl group, aC₁-C₂ alkoxy group, a C₁-C₂ alkyl group, or an oxygen atom bonded to asilicon atom of another comonomer.

Additionally or alternatively, each Z¹¹ can be a hydroxyl group, ethoxy,methoxy or an oxygen atom bonded to a silicon atom of another comonomer;and each Z¹² and Z¹³ independently can be a hydroxyl group, ethoxy,methyl, or an oxygen atom bonded to a silicon atom of another comonomer.

Additionally or alternatively, each Z¹¹ can be a hydroxyl group or anoxygen atom bonded to a silicon atom of another comonomer; and each Z¹²and Z¹³ independently can be a hydroxyl group, methyl, or an oxygen atombonded to a silicon atom of another comonomer.

Additionally or alternatively, each R² can be a C₁-C₈ alkylene group, aC₁-C₇ alkylene group, a C₁-C₆ alkylene group, a C₁-C₅ alkylene group, aC₁-C₄ alkylene group, a C₁-C₃ alkylene group, a C₁-C₂ alkylene group or—CH₂—.

Additionally or alternatively, each Z¹¹ can be a hydroxyl group, a C₁-C₂alkoxy group or an oxygen atom bonded to a silicon atom of anothercomonomer; each Z¹² and Z¹³ independently can be a hydroxyl group, aC₁-C₂ alkoxy group, a C₁-C₂ alkyl group, or an oxygen atom bonded to asilicon atom of another comonomer; and R² can be a C₁-C₄ alkylene group.

Additionally or alternatively, each R² can be a C₂-C₈ alkenylene group,a C₂-C₇ alkenylene group, a C₂-C₆ alkenylene group, a C₂-0₅ alkenylenegroup, a C₂-C₄ alkenylene group, a C₂-C₃ alkenylene group, or —HC═CH—.

Additionally or alternatively, each Z¹¹ can be a hydroxyl group, a C₁-C₂alkoxy group or an oxygen atom bonded to a silicon atom of anothercomonomer; each Z¹² and Z¹³ independently can be a hydroxyl group, aC₁-C₂ alkoxy group, a C₁-C₂ alkyl group, or an oxygen atom bonded to asilicon atom of another comonomer; and R² can be selected from the groupconsisting of a C₁-C₄ alkylene group and a C₂-C₄ alkenylene group.

Additionally or alternatively, each R² can be a C₂-C₈ alkynylene group,a C₂-C₇ alkynylene group, a C₂-C₆ alkynylene group, a C₂-C₅ alkynylenegroup, a C₂-C₄ alkynylene group, a C₂-C₃ alkynylene group, or —C≡C—.

Additionally or alternatively, each Z¹¹ can be a hydroxyl group, a C₁-C₂alkoxy group or an oxygen atom bonded to a silicon atom of anothercomonomer; each Z¹² and Z¹³ independently can be a hydroxyl group, aC₁-C₂ alkoxy group, a C₁-C₂ alkyl group, or an oxygen atom bonded to asilicon atom of another comonomer; and R² can be selected from the groupconsisting of a C ₁-C₄ alkylene group, a C₂-C₄ alkenylene group and aC₂-C₄ alkynylene group.

Additionally or alternatively, each R² can be a nitrogen-containingC₂-C₁₀ alkylene group, a nitrogen-containing C₃-C₁₀ alkylene group, anitrogen-containing C₄-C₁₀ alkylene group, a nitrogen-containing C₄-C₉alkylene group, a nitrogen-containing C₄-C₈ alkylene group, or nitrogencontaining C₃-C₈ alkylene group. The aforementioned nitrogen-containingalkylene groups may have one or more nitrogen atoms (e.g., 2, 3, etc.).Examples of nitrogen-containing alkylene groups include, but are notlimited to,

Additionally or alternatively, each Z¹¹ can be a hydroxyl group, a C₁-C₂alkoxy group or an oxygen atom bonded to a silicon atom of anothercomonomer; each Z¹² and Z¹³ independently can be a hydroxyl group, aC₁-C₂ alkoxy group, a C₁-C₂ alkyl group, or an oxygen atom bonded to asilicon atom of another comonomer; and each R² can be selected from thegroup consisting of a C₁-C₄ alkylene group, a C₂-C₄ alkenylene group, aC₂-C₄ alkynylene group and a nitrogen-containing C₄-C₁₀ alkylene group.

Additionally or alternatively, each R² can be an optionally substitutedC₆-C₂₀ aralkyl, an optionally substituted C₆-C₁₄ aralkyl, or anoptionally substituted C₆-C₁₀ aralkyl. Examples of C₆-C₂₀ aralkylsinclude, but are not limited to, phenylmethyl, phenylethyl, andnaphthylmethyl. The aralkyl may be optionally substituted with a C₁-C₆alkyl group, particularly a C₁-C₄ alkyl group.

Additionally or alternatively, each Z¹¹ can be a hydroxyl group, a C₁-C₂alkoxy group or an oxygen atom bonded to a silicon atom of anothercomonomer; each Z¹² and Z¹³ independently can be a hydroxyl group, aC₁-C₂ alkoxy group, a C₁-C₂ alkyl group, or an oxygen atom bonded to asilicon atom of another comonomer; and R² can be selected from the groupconsisting of a C₁-C₄ alkylene group, a C₂-C₄ alkenylene group, a C₂-C₄alkynylene group, a nitrogen-containing C₄-C₁₀ alkylene group and anoptionally substituted C₆-C₁₀ aralkyl.

Additionally or alternatively, each R² can be an optionally substitutedC₄-C₂₀ heterocycloalkyl group, an optionally substituted C₄-C₁₆heterocycloalkyl group, an optionally substituted C₄-C₁₂heterocycloalkyl group, or an optionally substituted C₄-C₁₀heterocycloalkyl group. Examples of C₄-C₂₀ heterocycloalkyl groupsinclude, but are not limited to, thienylmethyl, furylethyl,pyrrolylmethyl, piperazinylethyl, pyridylmethyl, benzoxazolylethyl,quinolinylpropyl, and imidazolylpropyl. The heterocycloalkyl may beoptionally substituted with a C₁-C₆ alkyl group, particularly a C₁-C₄alkyl group.

Additionally or alternatively, each Z¹¹ can be a hydroxyl group, a C₁-C₂alkoxy group or an oxygen atom bonded to a silicon atom of anothercomonomer; each Z¹² and Z¹³ independently can be a hydroxyl group, aC₁-C₂ alkoxy group, a C₁-C₂ alkyl group, or an oxygen atom bonded to asilicon atom of another comonomer; and each R² can be selected from thegroup consisting of a C₁-C₄ alkylene group, a C₂-C₄ alkenylene group, aC₂-C₄ alkynylene group, a nitrogen-containing C₄-C₁₀ alkylene group, anoptionally substituted C₆-C₁₀ aralkyl and an optionally substitutedC₄-C₁₀ heterocycloalkyl group.

Additionally or alternatively, each Z¹¹ can be a hydroxyl group, ethoxy,methoxy or an oxygen atom bonded to a silicon atom of another comonomer;each Z¹² and Z¹³ independently can be a hydroxyl group, ethoxy, methoxy,methyl, or an oxygen atom bonded to a silicon atom of another comonomer;and each R² can be selected from the group consisting of —CH₂—,—CH₂CH₂—, —HC═CH—,

Additionally or alternatively, each Z¹¹ can be a hydroxyl group or anoxygen atom bonded to a silicon atom of another comonomer; each Z¹² andZ¹³ independently can be a hydroxyl group, methyl, or an oxygen atombonded to a silicon atom of another comonomer; and each R² can beselected from the group consisting of —CH₂—,

In a particular embodiment, each Z¹¹ can be a hydroxyl group, ethoxy oran oxygen atom bonded to a silicon atom of another comonomer; each Z¹²can be a hydroxyl group, ethoxy, and an oxygen atom bonded to a siliconatom of another monomer; each Z¹³ can be methyl; and R² can be —CH₂CH₂—.

In another particular embodiment, each Z¹¹ can be a hydroxyl group,ethoxy or an oxygen atom bonded to a silicon atom of another comonomer;each Z¹² and Z¹³ independently can be selected from the group consistingof a hydroxyl group, ethoxy, and an oxygen atom bonded to a silicon atomof another monomer; and each R² can be —CH₂—.

In another particular embodiment, each Z¹¹ can be a hydroxyl group,ethoxy or an oxygen atom bonded to a silicon atom of another comonomer;each Z¹² and Z¹³ independently can be selected from the group consistingof a hydroxyl group, ethoxy, and an oxygen atom bonded to a silicon atomof another monomer; and each R² can be —HC═CH—.

In another particular embodiment, each Z¹¹ can be a hydroxyl group,methoxy or an oxygen atom bonded to a silicon atom of another comonomer;each Z¹² and Z¹³ independently can be selected from the group consistingof a hydroxyl group, methoxy, and an oxygen atom bonded to a siliconatom of another monomer; and each R² can be

In another particular embodiment, each Z¹¹ can be a hydroxyl group,ethoxy or an oxygen atom bonded to a silicon atom of another comonomer;each Z¹² can be a hydroxyl group, ethoxy, and an oxygen atom bonded to asilicon atom of another monomer; each Z¹³ can be methyl; and each R² canbe

In another particular embodiment, each Z¹¹ can be a hydroxyl group,methoxy or an oxygen atom bonded to a silicon atom of another comonomer;each Z¹² can be a hydroxyl group, methoxy, and an oxygen atom bonded toa silicon atom of another monomer; each Z¹³ can be methyl; and each R²can be

II.E. Monomers of Formula (V)

In various embodiments, the organosilica material may further compriseanother monomer in combination with independent units of Formula (I),such as at least one independent unit of Formula M¹(OZ¹⁴)₃ (V), whereinM¹ represents a Group 13 metal and each Z¹⁴ independently represents ahydrogen atom, a C₁-C₆ alkyl or a bond to a silicon atom of anothermonomer; and

Additionally or alternatively, M¹ can be B, Al, Ga, In, Tl, or Uut. Inparticular, M¹ can be Al or B.

Additionally or alternatively, each Z¹⁴ can be a hydrogen atom.

Additionally or alternatively, M¹ can be Al or B and each Z¹⁴ can be ahydrogen atom.

Additionally or alternatively, each Z¹⁴ can be a C₁-C₆ alkyl group, aC₁-C₅ alkyl group, a C₁-C₄ alkyl group, a C₁-C₃ alkyl group, a C₁-C₂alkyl group or methyl. In particular, each Z¹⁴ can be methyl, ethyl,propyl or butyl.

Additionally or alternatively, M¹ can be Al or B and each Z¹⁴ can be ahydrogen atom, methyl, ethyl, propyl or butyl.

Additionally or alternatively, each Z¹⁴ can be a bond to a silicon atomof another monomer.

Additionally or alternatively, M¹ can be Al or B and each Z¹⁴ can be ahydrogen atom, methyl, ethyl, propyl, butyl or a bond to a silicon atomof another monomer.

Additionally or alternatively, M¹ can be Al or B and each Z¹⁴ can be ahydrogen atom or a bond to a silicon atom of another monomer.

Additionally or alternatively, M¹ can be Al and each Z¹⁴ can be ahydrogen atom, methyl, ethyl, propyl, butyl or a bond to a silicon atomof another monomer.

In a particular embodiment, M¹ can be Al and each Z¹⁴ can be a hydrogenatom, methyl or a bond to a silicon atom of another monomer.

In another particular embodiment, M¹ can be Al and each Z¹⁴ can be ahydrogen atom, ethyl or a bond to a silicon atom of another monomer.

In another particular embodiment, M¹ can be Al and each Z¹⁴ can be ahydrogen atom, propyl or a bond to a silicon atom of another monomer.

In another particular embodiment, M¹ can be Al and each Z¹⁴ can be ahydrogen atom, butyl or a bond to a silicon atom of another monomer.

II.F. Monomers of Formula (VI)

In various embodiments, the organosilica material may further compriseanother monomer in combination with independent units of Formula (I),such as at least one independent unit of Formula (Z¹⁵O)₂M²-O—Si(OZ¹⁶)₃(VI), wherein M² represents a Group 13 metal and each Z¹⁵ and each Z¹⁶independently represent a hydrogen atom, a C₁-C₆ alkyl group or a bondto a silicon atom of another monomer.

Additionally or alternatively, M² can be B, Al, Ga, IN Tl, or Uut. Inparticular, M² can be Al or B.

Additionally or alternatively, each Z¹⁵ and/or each Z¹⁶ each can be ahydrogen atom.

Additionally or alternatively, M² can be Al or B and each Z¹⁵ and/oreach Z¹⁶ each can be a hydrogen atom.

Additionally or alternatively, each Z¹⁵ and/or each Z¹⁶ each can be aC₁-C₆ alkyl group, a C₁-C₅ alkyl group, a C₁-C₄ alkyl group, a C₁-C₃alkyl group, a C₁-C₂ alkyl group or methyl. In particular, each Z¹⁵and/or each Z¹⁶ each can be methyl, ethyl, propyl or butyl.

Additionally or alternatively, M² can be Al or B; and each Z¹⁵ and eachZ¹⁶ independently can be a hydrogen atom, methyl, ethyl, propyl orbutyl.

Additionally or alternatively, each Z¹⁵ and/or each Z¹⁶ each can be abond to a silicon atom of another monomer.

Additionally or alternatively, M² can be Al or B; and each Z¹⁵ and eachZ¹⁶ independently can be a hydrogen atom, methyl, ethyl, propyl, butylor a bond to a silicon atom of another monomer.

Additionally or alternatively, M² can be Al or B; each Z¹⁵ and each Z¹⁶independently can be a hydrogen atom or a bond to a silicon atom ofanother monomer.

Additionally or alternatively, M² can be Al; and each Z¹⁵ and each Z¹⁶independently can be a hydrogen atom, methyl, ethyl, propyl, butyl or abond to a silicon atom of another monomer.

In a particular embodiment, M² can be Al; and each Z¹⁵ and each Z¹⁶independently can be a hydrogen atom, methyl or a bond to a silicon atomof another monomer.

In another particular embodiment, M² can be Al; and each Z¹⁵ and eachZ¹⁶ independently can be a hydrogen atom, ethyl or a bond to a siliconatom of another monomer.

In another particular embodiment, M² can be Al; and each Z¹⁵ and eachZ¹⁶ independently can be a hydrogen atom, propyl or a bond to a siliconatom of another monomer.

In another particular embodiment, M² can be Al; and each Z¹⁵ and eachZ¹⁶ independently can be a hydrogen atom, butyl or a bond to a siliconatom of another monomer.

The organosilica materials made by the methods described herein can becharacterized as described in the following sections.

II.G. X-Ray Diffraction Peaks

The organosilica materials described herein can exhibit powder X-raydiffraction patterns with one peak between about 1 and about 4 degrees2θ, particularly one peak between about 1 and about 3 degrees 2θ orbetween about 1 and about 2 degrees 2θ. Additionally or alternatively,the organosilica materials can exhibit substantially no peaks in therange of about 0.5 to about 10 degrees 2θ, about 0.5 to about 12 degrees2θ range, about 0.5 to about 15 degrees 2θ, about 0.5 to about 20degrees 2θ, about 0.5 to about 30 degrees 2θ, about 0.5 to about 40degrees 2θ, about 0.5 to about 50 degrees 2θ, about 0.5 to about 60degrees 2θ, about 0.5 to about 70 degrees 2θ, about 2 to about 10degrees 2θ, about 2 to about 12 degrees 2θ range, about 2 to about 15degrees 2θ, about 2 to about 20 degrees 2θ, about 2 to about 30 degrees2θ, about 2 to about 40 degrees 2θ, about 2 to about 50 degrees 2θ,about 2 to about 60 degrees 2θ, about 2 to about 70 degrees 2θ, about 3to about 10 degrees 2θ, about 3 to about 12 degrees 2θ range, about 3 toabout 15 degrees 2θ, about 3 to about 20 degrees 2θ, about 3 to about 30degrees 2θ, about 3 to about 40 degrees 2θ, about 3 to about 50 degrees2θ, about 3 to about 60 degrees 2θ, or about 3 to about 70 degrees 2θ.

II.H. Silanol Content

The organosilica materials can have a silanol content that varies withinwide limits, depending on the composition of the synthesis solution. Thesilanol content can conveniently be determined by solid state siliconNMR.

In various aspects, the organosilica material can have a silanol contentof greater than about 5%, greater than about 10%, greater than about15%, greater than about 20%, greater than about 25%, greater than about30%, greater than about 33%, greater than 35%, greater than about 40%,greater than about 41%, greater than about 44%, greater than about 45%,greater than about 50%, greater than about 55%, greater than about 60%,greater than about 65%, greater than about 70%, greater than about 75%,or about 80%. In certain embodiments, the silanol content can be greaterthan about 30% or greater than about 41%.

Additionally or alternatively, the organosilica material may have asilanol content of about 5% to about 80%, about 5% to about 75%, about5% to about 70%, about 5% to about 65%, about 5% to about 60%, about 5%to about 55%, about 5% to about 50%, about 5% to about 45%, about 5% toabout 44%, about 5% to to about 41%, about 5% to about 40%, about 5% toabout 35%, about 5% to about 33%, about 5% to about 30%, about 5% toabout 25%, about 5% to about 20%, about 5% to about 15%, about 5% toabout 10%, about 10% to about 80%, about 10% to about 75%, about 10% toabout 70%, about 10% to about 65%, about 10% to about 60%, about 10% toabout 55%, about 10% to about 50%, about 10% to about 45%, about 10% toabout 44%, about 10% to about 41%, about 10% to about 40%, about 10% toabout 35%, about 10% to about 33%, about 10% to about 30%, about 10% toabout 25%, about 10% to about 20%, about 20% to about 80%, about 20% toabout 75%, about 20% to about 70%, about 20% to about 65%, about 20% toabout 60%, about 20% to about 55%, about 20% to about 50%, about 20% toabout 45%, about 20% to about 44%, about20% to about 41%, about 20% toabout 40%, about 20% to about 35%, about 20% to about 33%, about 20% toabout 30%, about 20% to about 25%, about 30% to about 80%, about 30% toabout 75%, about 30% to about 70%, about 30% to about 65%, about 30% toabout 60%, about 30% to about 55%, about 30% to about 50%, about 30% toabout 45%, about 30% to about 44%, about 30% to about 41%, about 30% toabout 40%, about 30% to about 35%, about 30% to about 33%, about 40% toabout 80%, about 40% to about 75%, about 40% to about 70%, about 40% toabout 65%, about 40% to about 60%, about 40% to about 55%, about 40% toabout 50%, about 40% to about 45%, about 40% to about 44%, or about 40%to about 41%.

II.I. Pore Size

The organosilica material described herein are advantageously in amesoporous form. As indicated previously, the term mesoporous refers tosolid materials having pores with a diameter within the range of fromabout 2 nm to about 50 nm. The average pore diameter of the organosilicamaterial can be determined, for example, using nitrogenadsorption-desorption isotherm techniques within the expertise of one ofskill in the art, such as the BET (Brunauer Emmet Teller) method.

The organosilica material can have an average pore diameter of about 0.2nm, about 0.4 nm, about 0.5 nm, about 0.6 nm, about 0.8 nm, about 1.0nm, about 1.5 nm, about 1.8 nm or less than about 2.0 nm.

Additionally or alternatively, the organosilica material canadvantageously have an average pore diameter within the mesopore rangeof about 2.0 nm, about 2.5 nm, about 3.0 nm, about 3.1 nm, about 3.2 nm,about 3.3 nm, about 3.4 nm, about 3.5 nm, about 3.6 nm, about 3.7 nm,about 3.8 nm, about 3.9 nm about 4.0 nm, about 4.1 nm, about 4.5 nm,about 5.0 nm, about 6.0 nm, about 7.0 nm, about 7.3 nm, about 8 nm,about 8.4 nm, about 9 nm, about 10 nm, about 11 nm, about 13 nm, about15 nm, about 18 nm, about 20 nm, about 23 nm, about 25 nm, about 30 nm,about 40 nm, about 45 nm, or about 50 nm.

Additionally or alternatively, the organosilica material can have anaverage pore diameter of 0.2 nm to about 50 nm, about 0.2 nm to about 40nm, about 0.2 nm to about 30 nm, about 0.2 nm to about 25 nm, about 0.2nm to about 23 nm, about 0.2 nm to about 20 nm, about 0.2 nm to about 18nm, about 0.2 nm to about 15 nm, about 0.2 nm to about 13 nm, about 0.2nm to about 11 nm, about 0.2 nm to about 10 nm, about 0.2 nm to about 9nm, about 0.2 nm to about 8.4 nm, about 0.2 nm to about 8 nm, about 0.2nm to about 7.3 nm, about 0.2 nm to about 7.0 nm, about 0.2 nm to about6.0 nm, about 0.2 nm to about 5.0 nm, about 0.2 nm to about 4.5 nm,about 0.2 nm to about 4.1 nm, about 0.2 nm to about 4.0 nm, about 0.2 nmto about 3.9 nm, about 0.2 nm to about 3.8 nm, about 0.2 nm to about 3.7nm, about 0.2 nm to about 3.6 nm, about 0.2 nm to about 3.5 nm, about0.2 nm to about 3.4 nm, about 0.2 nm to about 3.3 nm, about 0.2 nm toabout 3.2 nm, about 0.2 nm to about 3.1 nm, about 0.2 nm to about 3.0nm, about 0.2 nm to about 2.5 nm, about 0.2 nm to about 2.0 nm, about0.2 nm to about 1.0 nm, about 1.0 nm to about 50 nm, about 1.0 nm toabout 40 nm, about 1.0 nm to about 30 nm, about 1.0 nm to about 25 nm,about 1.0 nm to about 23 nm, about 1.0 nm to about 20 nm, about 1.0 nmto about 18 nm, about 1.0 nm to about 15 nm, about 1.0 nm to about 13nm, about 1.0 nm to about 11 nm, about 1.0 nm to about 10 nm, about 1.0nm to about 9 nm, about 1.0 nm to about 8.4 nm, about 1.0 nm to about 8nm, about 1.0 nm to about 7.3 nm, about 1.0 nm to about 7.0 nm, about1.0 nm to about 6.0 nm, about 1.0 nm to about 5.0 nm, about 1.0 nm toabout 4.5 nm, about 1.0 nm to about 4.1 nm, about 1.0 nm to about 4.0nm, about 1.0 nm to about 3.9 nm, about 1.0 nm to about 3.8 nm, about1.0 nm to about 3.7 nm, about 1.0 nm to about 3.6 nm, about 1.0 nm toabout 3.5 nm, about 1.0 nm to about 3.4 nm, about 1.0 nm to about 3.3nm, about 1.0 nm to about 3.2 nm, about 1.0 nm to about 3.1 nm, about1.0 nm to about 3.0 nm or about 1.0 nm to about 2.5 nm.

In particular, the organosilica material can advantageously have anaverage pore diameter in the mesopore range of about 2.0 nm to about 50nm, about 2.0 nm to about 40 nm, about 2.0 nm to about 30 nm, about 2.0nm to about 25 nm, about 2.0 nm to about 23 nm, about 2.0 nm to about 20nm, about 2.0 nm to about 18 nm, about 2.0 nm to about 15 nm, about 2.0nm to about 13 nm, about 2.0 nm to about 11 nm, about 2.0 nm to about 10nm, about 2.0 nm to about 9 nm, about 2.0 nm to about 8.4 nm, about 2.0nm to about 8 nm, about 2.0 nm to about 7.3 nm, about 2.0 nm to about7.0 nm, about 2.0 nm to about 6.0 nm, about 2.0 nm to about 5.0 nm,about 2.0 nm to about 4.5 nm, about 2.0 nm to about 4.1 nm, about 2.0 nmto about 4.0 nm, about 2.0 nm to about 3.9 nm, about 2.0 nm to about 3.8nm, about 2.0 nm to about 3.7 nm, about 2.0 nm to about 3.6 nm, about2.0 nm to about 3.5 nm, about 2.0 nm to about 3.4 nm, about 2.0 nm toabout 3.3 nm, about 2.0 nm to about 3.2 nm, about 2.0 nm to about 3.1nm, about 2.0 nm to about 3.0 nm, about 2.0 nm to about 2.5 nm, about2.5 nm to about 50 nm, about 2.5 nm to about 40 nm, about 2.5 nm toabout 30 nm, about 2.5 nm to about 25 nm, about 2.5 nm to about 23 nm,about 2.5 nm to about 20 nm, about 2.5 nm to about 18 nm, about 2.5 nmto about 15 nm, about 2.5 nm to about 13 nm, about 2.5 nm to about 11nm, about 2.5 nm to about 10 nm, about 2.5 nm to about 9 nm, about 2.5nm to about 8.4 nm, about 2.5 nm to about 8 nm, about 2.5 nm to about7.3 nm, about 2.5 nm to about 7.0 nm, about 2.5 nm to about 6.0 nm,about 2.5 nm to about 5.0 nm, about 2.5 nm to about 4.5 nm, about 2.5 nmto about 4.1 nm, about 2.5 nm to about 4.0 nm, about 2.5 nm to about 3.9nm, about 2.5 nm to about 3.8 nm, about 2.5 nm to about 3.7 nm, about2.5 nm to about 3.6 nm, about 2.5 nm to about 3.5 nm, about 2.5 nm toabout 3.4 nm, about 2.5 nm to about 3.3 nm, about 2.5 nm to about 3.2nm, about 2.5 nm to about 3.1 nm, about 2.5 nm to about 3.0 nm, about3.0 nm to about 50 nm, about 3.0 nm to about 40 nm, about 3.0 nm toabout 30 nm, about 3.0 nm to about 25 nm, about 3.0 nm to about 23 nm,about 3.0 nm to about 20 nm, about 3.0 nm to about 18 nm, about 3.0 nmto about 15 nm, about 3.0 nm to about 13 nm, about 3.0 nm to about 11nm, about 3.0 nm to about 10 nm, about 3.0 nm to about 9 nm, about 3.0nm to about 8.4 nm, about 3.0 nm to about 8 nm, about 3.0 nm to about7.3 nm, about 3.0 nm to about 7.0 nm, about 3.0 nm to about 6.0 nm,about 3.0 nm to about 5.0 nm, about 3.0 nm to about 4.5 nm, about 3.0 nmto about 4.1 nm, or about 3.0 nm to about 4.0 nm.

In one particular embodiment, the organosilica material described hereincan have an average pore diameter of about 1.0 nm to about 30.0 nm,particularly about 1.0 nm to about 25.0 nm, particularly about 1.5 nm toabout 25.0 nm, particularly about 2.0 nm to about 25.0 nm, particularlyabout 2.0 nm to about 20.0 nm, particularly about 2.0 nm to about 15.0nm, or particularly about 2.0 nm to about 10.0 nm.

Using surfactant as a template to synthesize mesoporous materials cancreate highly ordered structure, e.g. well-defined cylindrical-like porechannels. In some circumstances, there may be no hysteresis loopobserved from N₂ adsorption isotherm. In other circumstances, forinstance where mesoporous materials can have less ordered porestructures, a hysteresis loop may be observed from N2 adsorptionisotherm experiments. In such circumstances, without being bound bytheory, the hysteresis can result from the lack of regularity in thepore shapes/sizes and/or from bottleneck constrictions in such irregularpores.

II.J. Surface Area

The surface area of the organosilica material can be determined, forexample, using nitrogen adsorption-desorption isotherm techniques withinthe expertise of one of skill in the art, such as the BET (BrunauerEmmet Teller) method. This method may determine a total surface area, anexternal surface area, and a microporous surface area. As used herein,and unless otherwise specified, “total surface area” refers to the totalsurface area as determined by the BET method. As used herein, and unlessotherwise specified, “microporous surface area” refers to microporoussurface are as determined by the BET method.

In various embodiments, the organosilica material can have a totalsurface area greater than or equal to about 100 m²/g, greater than orequal to about 200 m²/g, greater than or equal to about 300 m²/g,greater than or equal to about 400 m²/g, greater than or equal to about450 m²/g, greater than or equal to about 500 m²/g, greater than or equalto about 550 m²/g, greater than or equal to about 600 m²/g, greater thanor equal to about 700 m²/g, greater than or equal to about 800 m²/g,greater than or equal to about 850 m²/g, greater than or equal to about900 m²/g, greater than or equal to about 1,000 m²/g, greater than orequal to about 1,050 m²/g, greater than or equal to about 1,100 m²/g,greater than or equal to about 1,150 m²/g, greater than or equal toabout 1,200 m²/g, greater than or equal to about 1,250 m²/g, greaterthan or equal to about 1,300 m²/g, greater than or equal to about 1,400m²/g, greater than or equal to about 1,450 m²/g, greater than or equalto about 1,500 m²/g, greater than or equal to about 1,550 m²/g, greaterthan or equal to about 1,600 m²/g, greater than or equal to about 1,700m²/g, greater than or equal to about 1,800 m²/g, greater than or equalto about 1,900 m²/g, greater than or equal to about 2,000 m²/g, greaterthan or equal to greater than or equal to about 2,100 m²/g, greater thanor equal to about 2,200 m²/g, greater than or equal to about 2,300 m²/gor about 2,500 m²/g.

Additionally or alternatively, the organosilica material may have atotal surface area of about 50 m²/g to about 2,500 m²/g, about 50 m²/gto about 2,000 m²/g, about 50 m²/g to about 1,500 m²/g, about 50 m²/g toabout 1,000 m²/g, about 100 m²/g to about 2,500 m²/g, about 100 m²/g toabout 2,300 m²/g, about 100 m²/g to about 2,200 m²/g, about 100 m²/g toabout 2,100 m²/g, about 100 m²/g to about 2,000 m²/g, about 100 m²/g toabout 1,900 m²/g, about 100 m²/g to about 1,800 m²/g, about 100 m²/g toabout 1,700 m²/g, about 100 m²/g to about 1,600 m²/g, about 100 m²/g toabout 1,550 m²/g, about 100 m²/g to about 1,500 m²/g, about 100 m²/g toabout 1,450 m²/g, about 100 m²/g to about 1,400 m²/g, about 100 m²/g toabout 1,300 m²/g, about 100 m²/g to about 1,250 m²/g, about 100 m²/g toabout 1,200 m²/g, about 100 m²/g to about 1,150 m²/g, about 100 m²/g toabout 1,100 m²/g, about 100 m²/g to about 1,050 m2/g, about 100 m²/g toabout 1,000 m²/g, about 100 m²/g to about 900 m²/g, about 100 m²/g toabout 850 m²/g, about 100 m²/g to about 800 m²/g, about 100 m²/g toabout 700 m²/g, about 100 m²/g to about 600 m²/g, about 100 m²/g toabout 550m²/g, about 100 m²/g to about 500 m²/g, about 100 m²/g to about450 m²/g, about 100 m²/g to about 400 m²/g, about 100 m²/g to about 300m²/g, about 100 m²/g to about 200 m²/g, about 200 m²/g to about 2,500m²/g, about 200 m²/g to about 2,300 m²/g, about 200 m²/g to about 2,200m²/g, about 200 m²/g to about 2,100 m²/g, about 200 m²/g to about 2,000m²/g, about 200 m²/g to about 1,900 m²/g, about 200 m²/g to about 1,800m²/g, about 200 m²/g to about 1,700 m²/g, about 200 m²/g to about 1,600m²/g, about 200 m²/g to about 1,550 m²/g, about 200 m²/g to about 1,500m²/g, about 200 m²/g to about 1,450 m²/g, about 200 m²/g to about 1,400m²/g, about 200 m²/g to about 1,300 m²/g, about 200 m²/g to about 1,250m²/g, about 200 m²/g to about 1,200 m²/g, about 200 m²/g to about 1,150m²/g, about 200 m²/g to about 1,100 m²/g, about 200 m²/g to about 1,050m²/g, about 200 m²/g to about 1,000 m²/g, about 200 m²/g to about 900m²/g, about 200 m²/g to about 850 m²/g, about 200 m²/g to about 800m²/g, about 200 m²/g to about 700 m²/g, about 200 m²/g to about 600m²/g, about 200 m²/g to about 550 m²/g, about 200 m²/g to about 500m²/g, about 200 m²/g to about 450 m²/g, about 200 m²/g to about 400m²/g, about 200 m²/g to about 300 m²/g, about 500 m²/g to about 2,500m²/g, about 500 m²/g to about 2,300 m²/g, about 500 m²/g to about 2,200m²/g, about 500 m²/g to about 2,100 m²/g, about 500 m²/g to about 2,000m²/g, about 500 m²/g to about 1,900 m²/g, about 500 m²/g to about 1,800m²/g, about 500 m²/g to about 1,700 m²/g, about 500 m²/g to about 1,600m²/g, about 500 m²/g to about 1,550 m²/g, about 500 m²/g to about 1,500m²/g, about 500 m²/g to about 1,450 m²/g, about 500 m²/g to about 1,400m²/g, about 500 m²/g to about 1,300 m²/g, about 500 m²/g to about 1,250m²/g, about 500 m²/g to about 1,200 m²/g, about 500 m²/g to about 1,150m²/g, about 500 m²/g to about 1,100 m²/g, about 500 m²/g to about 1,050m²/g, about 500 m²/g to about 1,000 m²/g, about 500 m²/g to about 900m²/g, about 500 m²/g to about 850 m²/g, about 500 m²/g to about 800m²/g, about 500 m²/g to about 700 m²/g, about 500 m²/g to about 600m²/g, about 500 m²/g to about 550m²/g, about 1,000 m²/g to about 2,500m²/g, about 1,000 m²/g to about 2,300 m²/g, about 1,000 m²/g to about2,200 m²/g, about 1,000 m²/g to about 2,100 m²/g, about 1,000 m²/g toabout 2,000 m²/g, about 1,000 m²/g to about 1,900 m²/g, about 1,000 m²/gto about 1,800 m²/g, about 1,000 m²/g to about 1,700 m²/g, about 1,000m²/g to about 1,600 m²/g, about 1,000 m²/g to about 1,550 m²/g, about1,000 m²/g to about 1,500 m²/g, about 1,000 m²/g to about 1,450 m²/g,about 1,000 m²/g to about 1,400 m²/g, about 1,000 m²/g to about 1,300m²/g, about 1,000 m²/g to about 1,250 m²/g, about 1,000 m²/g to about1,200 m²/g, about 1,000 m²/g to about 1,150 m²/g, about 1,000 m²/g toabout 1,100 m²/g, or about 1,000 m²/g to about 1,050 m²/g.

In one particular embodiment, the organosilica material described hereinmay have a total surface area of about 200 m²/g to about 2,500 m²g,particularly about 400 m²/g to about 2,500 m²g, particularly about 400m²/g to about 2,000 m²/g, or particularly about 400 m²/g to about 1,500m²/g.

II.K. Pore Volume

The pore volume of the organosilica material made by the methodsdescribed herein can be determined, for example, using nitrogenadsorption-desorption isotherm techniques within the expertise of one ofskill in the art, such as the BET (Brunauer Emmet Teller) method.

In various embodiments, the organosilica material can have a pore volumegreater than or equal to about 0.1 cm³/g, greater than or equal to about0.2 cm³/g, greater than or equal to about 0.3 cm³/g, greater than orequal to about 0.4 cm³/g, greater than or equal to about 0.5 cm³/g,greater than or equal to about 0.6 cm³/g, greater than or equal to about0.7 cm³/g, greater than or equal to about 0.8 cm³/g, greater than orequal to about 0.9 cm³/g, greater than or equal to about 1.0 cm³/g,greater than or equal to about 1.1 cm³/g, greater than or equal to about1.2 cm³/g, greater than or equal to about 1.3 cm³/g, greater than orequal to about 1.4 cm³/g, greater than or equal to about 1.5 cm³/g,greater than or equal to about 1.6 cm³/g, greater than or equal to about1.7 cm³/g, greater than or equal to about 1.8 cm³/g, greater than orequal to about 1.9 cm³/g, greater than or equal to about 2.0 cm³/g,greater than or equal to about 2.5 cm³/g, greater than or equal to about3.0 cm³/g, greater than or equal to about 3.5 cm³/g, greater than orequal to about 4.0 cm³/g, greater than or equal to about 5.0 cm³/g,greater than or equal to about 6.0 cm³/g, greater than or equal to about7.0 cm³/g, or about 10.0 cm³/g.

Additionally or alternatively, the organosilica material can have a porevolume of about 0.1 cm³/g to about 10.0 cm³/g, about 0.1 cm³/g to about7.0 cm³/g, about 0.1 cm³/g to about 6.0 cm³/g, about 0.1 cm³/g to about5.0 cm³/g, about 0.1 cm³/g to about 4.0 cm³/g, about 0.1 cm³/g to about3.5 cm³/g, about 0.1 cm³/g to about 3.0 cm³/g, about 0.1 cm³/g to about2.5 cm³/g, about 0.1 cm³/g to about 2.0 cm³/g, about 0.1 cm³/g to about1.9 cm³/g, about 0.1 cm³/g to about 1.8 cm³/g, about 0.1 cm³/g to about1.7 cm³/g, about 0.1 cm³/g to about 1.6 cm³/g, about 0.1 cm³/g to about1.5 cm³/g, about 0.1 cm³/g to about 1.4 cm³/g, about 0.1 cm³/g to about1.3 cm³/g, about 0.1 cm³/g to about 1.2 cm³/g, about 0.1 cm³/g to about1.1, about 0.1 cm³/g to about 1.0 cm³/g, about 0.1 cm³/g to about 0.9cm³/g, about 0.1 cm³/g to about 0.8 cm³/g, about 0.1 cm³/g to about 0.7cm³/g, about 0.1 cm³/g to about 0.6 cm³/g, about 0.1 cm³/g to about 0.5cm³/g, about 0.1 cm³/g to about 0.4 cm³/g, about 0.1 cm³/g to about 0.3cm³/g, about 0.1 cm³/g to about 0.2 cm³/g, 0.2 cm³/g to about 10.0cm³/g, about 0.2 cm³/g to about 7.0 cm³/g, about 0.2 cm³/g to about 6.0cm³/g, about 0.2 cm³/g to about 5.0 cm³/g, about 0.2 cm³/g to about 4.0cm³/g, about 0.2 cm³/g to about 3.5 cm³/g, about 0.2 cm³/g to about 3.0cm³/g, about 0.2 cm³/g to about 2.5 cm³/g, about 0.2 cm³/g to about 2.0cm³/g, about 0.2 cm³/g to about 1.9 cm³/g, about 0.2 cm³/g to about 1.8cm³/g, about 0.2 cm³/g to about 1.7 cm³/g, about 0.2 cm³/g to about 1.6cm³/g, about 0.2 cm³/g to about 1.5 cm³/g, about 0.2 cm³/g to about 1.4cm³/g, about 0.2 cm³/g to about 1.3 cm³/g, about 0.2 cm³/g to about 1.2cm³/g, about 0.2 cm³/g to about 1.1, about 0.5 cm³/g to about 1.0 cm³/g,about 0.5 cm³/g to about 0.9 cm³/g, about 0.5 cm³/g to about 0.8 cm³/g,about 0.5 cm³/g to about 0.7 cm³/g, about 0.5 cm³/g to about 0.6 cm³/g,about 0.5 cm³/g to about 0.5 cm³/g, about 0.5 cm³/g to about 0.4 cm³/g,about 0.5 cm³/g to about 0.3 cm³/g, 0.5 cm³/g to about 10.0 cm³/g, about0.5 cm³/g to about 7.0 cm³/g, about 0.5 cm³/g to about 6.0 cm³/g, about0.5 cm³/g to about 5.0 cm³/g, about 0.5 cm³/g to about 4.0 cm³/g, about0.5 cm³/g to about 3.5 cm³/g, about 0.5 cm³/g to about 3.0 cm³/g, about0.5 cm³/g to about 2.5 cm³/g, about 0.5 cm³/g to about 2.0 cm³/g, about0.5 cm³/g to about 1.9 cm³/g, about 0.5 cm³/g to about 1.8 cm³/g, about0.5 cm³/g to about 1.7 cm³/g, about 0.5 cm³/g to about 1.6 cm³/g, about0.5 cm³/g to about 1.5 cm³/g, about 0.5 cm³/g to about 1.4 cm³/g, about0.5 cm³/g to about 1.3 cm³/g, about 0.5 cm³/g to about 1.2 cm³/g, about0.5 cm³/g to about 1.1, about 0.5 cm³/g to about 1.0 cm³/g, about 0.5cm³/g to about 0.9 cm³/g, about 0.5 cm³/g to about 0.8 cm³/g, about 0.5cm³/g to about 0.7 cm³/g, or about 0.5 cm³/g to about 0.6 cm³/g.

In a particular embodiment, the organosilica material can have a porevolume of about 0.1 cm³/g to about 5.0 cm³/g, particularly about 0.1cm³/g to about 3.0 cm³/g, particularly about 0.2 cm³/g to about 3.0cm³/g, particularly about 0.2 cm³/g to about 2.5 cm³/g, or particularlyabout 0.2 cm³/g to about 1.5 cm³/g.

II.L. Additional Metals

In some embodiments, the organosilica material can further comprise atleast one catalyst metal incorporated within the pores of theorganosilica material. Exemplary catalyst metals can include, but arenot limited to, a Group 6 element, a Group 8 element, a Group 9 element,a Group 10 element or a combination thereof. Exemplary Group 6 elementscan include, but are not limited to, chromium, molybdenum, and/ortungsten, particularly including molybdenum and/or tungsten. ExemplaryGroup 8 elements can include, but are not limited to, iron, ruthenium,and/or osmium. Exemplary Group 9 elements can include, but are notlimited to, cobalt, rhodium, and/or iridium, particularly includingcobalt. Exemplary Group 10 elements can include, but are not limited to,nickel, palladium and/or platinum.

The catalyst metal can be incorporated into the organosilica material byany convenient method, such as by impregnation, by ion exchange, or bycomplexation to surface sites. The catalyst metal so incorporated may beemployed to promote any one of a number of catalytic tranformationscommonly conducted in petroleum refining or petrochemicals production.Examples of such catalytic processes can include, but are not limitedto, hydrogenation, dehydrogenation, aromatization, aromatic saturation,hydrodesulfurization, olefin oligomerization, polymerization,hydrodenitrogenation, hydrocracking, naphtha reforming, paraffinisomerization, aromatic transalkylation, saturation of double/triplebonds, and the like, as well as combinations thereof.

Thus, in another embodiment, a catalyst material comprising theorganosilica material described herein is provided. The catalystmaterial may optionally comprise a binder or be self-bound. Suitablebinders, include but are not limited to active and inactive materials,synthetic or naturally occurring zeolites, as well as inorganicmaterials such as clays and/or oxides such as silica, alumina, zirconia,titania, silica-alumina, cerium oxide, magnesium oxide, or combinationsthereof. In particular, the binder may be silica-alumina, alumina and/ora zeolite, particularly alumina. Silica-alumina may be either naturallyoccurring or in the form of gelatinous precipitates or gels includingmixtures of silica and metal oxides. It should be noted it is recognizedherein that the use of a material in conjunction with a zeolite bindermaterial, i.e., combined therewith or present during its synthesis,which itself is catalytically active may change the conversion and/orselectivity of the finished catalyst. It is also recognized herein thatinactive materials can suitably serve as diluents to control the amountof conversion if the present invention is employed in alkylationprocesses so that alkylation products can be obtained economically andorderly without employing other means for controlling the rate ofreaction. These inactive materials may be incorporated into naturallyoccurring clays, e.g., bentonite and kaolin, to improve the crushstrength of the catalyst under commercial operating conditions andfunction as binders or matrices for the catalyst. The catalystsdescribed herein typically can comprise, in a composited form, a ratioof support material to binder material of about 100 parts supportmaterial to about zero parts binder material; about 99 parts supportmaterial to about 1 parts binder material; about 95 parts supportmaterial to about 5 parts binder material. Additionally oralternatively, the catalysts described herein typically can comprise, ina composited form, a ratio of support material to binder materialranging from about 90 parts support material to about 10 parts bindermaterial to about 10 parts support material to about 90 parts bindermaterial; about 85 parts support material to about 15 parts bindermaterial to about 15 parts support material to about 85 parts bindermaterial; about 80 parts support material to 20 parts binder material to20 parts support material to 80 parts binder material, all ratios beingby weight, typically from 80:20 to 50:50 support material:bindermaterial, preferably from 65:35 to 35:65. Compositing may be done byconventional means including mulling the materials together followed byextrusion of pelletizing into the desired finished catalyst particles.

In some embodiments, the organosilica material can further comprisecationic metal sites incorporated into the network structure. Suchcationic metal sites may be incorporated by any convenient method, suchas impregnation or complexation to the surface, through an organicprecursor, or by some other method. This organometallic material may beemployed in a number of hydrocarbon separations conducted in petroleumrefining or petrochemicals production. Examples of such compounds to bedesirably separated from petrochemicals/fuels can include olefins,paraffins, aromatics, and the like.

Additionally or alternatively, the organosilica material can furthercomprise a surface metal incorporated within the pores of theorganosilica material. The surface metal can be selected from a Group 1element, a Group 2 element, a Group 13 element, and a combinationthereof. When a Group 1 element is present, it can preferably compriseor be sodium and/or potassium. When a Group 2 element is present, it caninclude, but may not be limited to, magnesium and/or calcium. When aGroup 13 element is present, it can include, but may not be limited to,boron and/or aluminum.

One or more of the Group 1, 2, 6, 8-10 and/or 13 elements may be presenton an exterior and/or interior surface of the organosilica material. Forexample, one or more of the Group 1, 2 and/or 13 elements may be presentin a first layer on the organosilica material and one or more of theGroup 6, 8, 9 and/or 10 elements may be present in a second layer, e.g.,at least partially atop the Group 1, 2 and/or 13 elements. Additionallyor alternatively, only one or more Group 6, 8, 9 and/or 10 elements maypresent on an exterior and/or interior surface of the organosilicamaterial. The surface metal(s) can be incorporated into/onto theorganosilica material by any convenient method, such as by impregnation,deposition, grafting, co-condensation, by ion exchange, and/or the like.

III. Methods of Making Organosilica Materials

In another embodiment, methods of producing the organosilica materialdescribed herein are provided. The method comprises:

(a) providing an aqueous mixture that contains essentially no structuredirecting agent and/or porogen;

(b) adding at least one cyclic compound of Formula

into the aqueous mixture to form a solution, wherein each R³independently can be a X¹OX²X³SiX⁴ group, wherein each X¹ can be a C₁-C₄alkyl group; each X² and X³ independently can be a C₁-C₄ alkyl group ora C₁-C₄ alkoxy group; and each X⁴ can be a C₁-C₈ alkylene group bondedto a nitrogen atom of the cyclic compound;

(c) aging the solution to produce a pre-product; and

(d) drying the pre-product to obtain an organosilica material which is apolymer comprising at least one independent cyclic urea monomer ofFormula (I) as described herein.

Additionally or alternatively, the at least one compound of Formula (Ia)can be added in step (b) as at least partially hydroxylated and/or as atleast partially polymerized/oligomerized, such that each X¹ can morebroadly represent a hydrogen, a C₁-C₄ alkyl group or an oxygen atombonded to a silicon atom of another siloxane and each X² and X³ can morebroadly represent a hydroxyl group, a C₁-C₄ alkoxy group, a C₁-C₄ alkylgroup, or an oxygen atom bonded to a silicon atom of anothersiloxane/monomer. In other words, an unaged pre-product can be added instep (b), in addition to or as an alternative to the monomeric (at leastone) compound of Formula (Ia).

III.A. Aqueous Mixture

The organosilica materials described herein may be made usingessentially no structure directing agent or porogen. Thus, the aqueousmixture contains essentially no added structure directing agent and/orno added porogen.

As used herein, “no added structure directing agent,” and “no addedporogen” means either (i) there is no component present in the synthesisof the organosilica material that aids in and/or guides thepolymerization and/or polycondensing and/or organization of the buildingblocks that form the framework of the organosilica material; or (ii)such component is present in the synthesis of the organosilica materialin a minor, or a non-substantial, or a negligible amount such that thecomponent cannot be said to aid in and/or guide the polymerizationand/or polycondensing and/or organization of the building blocks thatform the framework of the organosilica material. Further, “no addedstructure directing agent” is synonymous with “no added template” and“no added templating agent.”

1. Structure Directing Agent

Examples of a structure directing agent can include, but are not limitedto, non-ionic surfactants, ionic surfactants, cationic surfactants,silicon surfactants, amphoteric surfactants, polyalkylene oxidesurfactants, fluorosurfactants, colloidal crystals, polymers, hyperbranched molecules, star-shaped molecules, macromolecules, dendrimers,and combinations thereof. Additionally or alternatively, the surfacedirecting agent can comprise or be a poloxamer, a triblock polymer, atetraalkylammonium salt, a nonionic polyoxyethylene alkyl, a Geminisurfactant, or a mixture thereof. Examples of a tetraalkylammonium saltcan include, but are not limited to, cetyltrimethylammonium halides,such as cetyltrimethylammonium chloride (CTAC), cetyltrimethylammoniumbromide (CTAB), and octadecyltrimethylammonium chloride. Other exemplarysurface directing agents can additionally or alternatively includehexadecyltrimethylammonium chloride and/or cetylpyridinium bromide.

Poloxamers are block copolymers of ethylene oxide and propylene oxide,more particularly nonionic triblock copolymers composed of a centralhydrophobic chain of polyoxypropylene (poly(propylene oxide)) flanked bytwo hydrophilic chains of polyoxyethylene (poly(ethylene oxide)).Specifically, the term “poloxamer” refers to a polymer having theformula HO(C₂H₄))a(C₃H₆O)_(b)(C₂H₄O)_(a)H in which “a” and “b” denotethe number of polyoxyethylene and polyoxypropylene units, respectively.Poloxamers are also known by the trade name Pluronic®, for examplePluronic® 123 and Pluronic®F 127. An additional triblock polymer isB50-6600.

Nonionic polyoxyethylene alkyl ethers are known by the trade name Brij®,for example Brij® 56, Brij® 58, Brij® 76, Brij ® 78. Gemini surfactantsare compounds having at least two hydrophobic groups and at least one oroptionally two hydrophilic groups per molecule have been introduced.

2. Porogen

A porogen material is capable of forming domains, discrete regions,voids and/or pores in the organosilica material. An example of a porogenis a block copolymer (e.g., a di-block polymer). As used herein, porogendoes not include water. Examples of polymer porogens can include, butare not limited to, polyvinyl aromatics, such as polystyrenes,polyvinylpyridines, hydrogenated polyvinyl aromatics,polyacrylonitriles, polyalkylene oxides, such as polyethylene oxides andpolypropylene oxides, polyethylenes, polylactic acids, polysiloxanes,polycaprolactones, polycaprolactams, polyurethanes, polymethacrylates,such as polymethylmethacrylate or polymethacrylic acid, polyacrylates,such as polymethylacrylate and polyacrylic acid, polydienes such aspolybutadienes and polyisoprenes, polyvinyl chlorides, polyacetals, andamine-capped alkylene oxides, as well as combinations thereof.

Additionally or alternatively, porogens can be thermoplastichomopolymers and random (as opposed to block) copolymers. As usedherein, “homopolymer” means compounds comprising repeating units from asingle monomer. Suitable thermoplastic materials can include, but arenot limited to, homopolymers or copolymers of polystyrenes,polyacrylates, polymethacrylates, polybutadienes, polyisoprenes,polyphenylene oxides, polypropylene oxides, polyethylene oxides,poly(dimethylsiloxanes), polytetrahydrofurans, polyethylenes,polycyclohexylethylenes, polyethyloxazolines, polyvinylpyridines,polycaprolactones, polylactic acids, copolymers of these materials andmixtures of these materials. Examples of polystyrene include, but arenot limited to anionic polymerized polystyrene, syndiotacticpolystyrene, unsubstituted and substituted polystyrenes (for example,poly(α-methyl styrene)). The thermoplastic materials may be linear,branched, hyperbranched, dendritic, or star like in nature.

Additionally or alternatively, the porogen can be a solvent. Examples ofsolvents can include, but are not limited to, ketones (e.g.,cyclohexanone, cyclopentanone, 2-heptanone, cycloheptanone,cyclooctanone, cyclohexylpyrrolidinone, methyl isobutyl ketone, methylethyl ketone, acetone), carbonate compounds (e.g., ethylene carbonate,propylene carbonate), heterocyclic compounds (e.g.,3-methyl-2-oxazolidinone, dimethylimidazolidinone, N-methylpyrrolidone,pyridine), cyclic ethers (e.g., dioxane, tetrahydrofuran), chain ethers(e.g., diethyl ether, ethylene glycol dimethyl ether, propylene glycoldimethyl ether, tetraethylene glycol dimethyl ether, polyethylene glycoldimethyl ether, ethylene glycol monomethyl ether, ethylene glycolmonoethyl ether, propylene glycol monomethyl ether (PGME), triethyleneglycol monobutyl ether, propylene glycol monopropyl ether, triethyleneglycol monomethyl ether, diethylene glycol ethyl ether, diethyleneglycol methyl ether, dipropylene glycol methyl ether, dipropylene glycoldimethyl ether, propylene glycol phenyl ether, tripropylene glycolmethyl ether), alcohols (e.g., methanol, ethanol), polyhydric alcohols(e.g., ethylene glycol, propylene glycol, polyethylene glycol,polypropylene glycol, glycerin, dipropylene glycol), nitrile compounds(e.g., acetonitrile, glutarodinitrile, methoxyacetonitrile,propionitrile, benzonitrile), esters (e.g., ethyl acetate, butylacetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethylethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate,2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate,propylene glycol monomethyl ether acetate (PGMEA), butyrolactone,phosphoric acid ester, phosphonic acid ester), aprotic polar substances(e.g., dimethyl sulfoxide, sulfolane, dimethylformamide,dimethylacetamide), nonpolar solvents (e.g., toluene, xylene,mesitylene), chlorine-based solvents (e.g., methylene dichloride,ethylene dichloride), benzene, dichlorobenzene, naphthalene, diphenylether, diisopropylbenzene, triethylamine, methyl benzoate, ethylbenzoate, butyl benzoate, monomethyl ether acetate hydroxy ethers suchas dibenzylethers, diglyme, triglyme, and mixtures thereof.

3. Base/Acid

In various embodiments, the aqueous mixture used in methods providedherein can comprise a base and/or an acid.

In certain embodiments where the aqueous mixture comprises a base, theaqueous mixture can have a pH from about 8 to about 15, from about 8 toabout 14.5, from about 8 to about 14, from about 8 to about 13.5, fromabout 8 to about 13, from about 8 to about 12.5, from about 8 to about12, from about 8 to about 11.5, from about 8 to about 11, from about 8to about 10.5, from about 8 to about 10, from about 8 to about 9.5, fromabout 8 to about 9, from about 8 to about 8.5, from about 8.5 to about15, from about 8.5 to about 14.5, from about 8.5 to about 14, from about8.5 to about 13.5, from about 8.5 to about 13, from about 8.5 to about12.5, from about 8.5 to about 12, from about 8.5 to about 11.5, fromabout 8.5 to about 11, from about 8.5 to about 10.5, from about 8.5 toabout 10, from about 8.5 to about 9.5, from about 8.5 to about 9, fromabout 9 to about 15, from about 9 to about 14.5, from about 9 to about14, from about 9 to about 13.5, from about 9 to about 13, from about 9to about 12.5, from about 9 to about 12, from about 9 to about 11.5,from about 9 to about 11, from about 9 to about 10.5, from about 9 toabout 10, from about 9 to about 9.5, from about 9.5 to about 15, fromabout 9.5 to about 14.5, from about 9.5 to about 14, from about 9.5 toabout 13.5, from about 9.5 to about 13, from about 9.5 to about 12.5,from about 9.5 to about 12, from about 9.5 to about 11.5, from about 9.5to about 11, from about 9.5 to about 10.5, from about 9.5 to about 10,from about 10 to about 15, from about 10 to about 14.5, from about 10 toabout 14, from about 10 to about 13.5, from about 10 to about 13, fromabout 10 to about 12.5, from about 10 to about 12, from about 10 toabout 11.5, from about 10 to about 11, from about 10 to about 10.5, fromabout 10.5 to about 15, from about 10.5 to about 14.5, from about 10.5to about 14, from about 10.5 to about 13.5, from about 10.5 to about 13,from about 10.5 to about 12.5, from about 10.5 to about 12, from about10.5 to about 11.5, from about 10.5 to about 11, from about 11 to about15, from about 11 to about 14.5, from about 11 to about 14, from about11 to about 13.5, from about 11 to about 13, from about 11 to about12.5, from about 11 to about 12, from about 11 to about 11.5, from about11.5 to about 15, from about 11.5 to about 14.5, from about 11.5 toabout 14, from about 11.5 to about 13.5, from about 11.5 to about 13,from about 11.5 to about 12.5, from about 11.5 to about 12, from about12 to about 15, from about 12 to about 14.5, from about 12 to about 14,from about 12 to about 13.5, from about 12 to about 13, from about 12 toabout 12.5, from about 12.5 to about 15, from about 12.5 to about 14.5,from about 12.5 to about 14, from about 12.5 to about 13.5, from about12.5 to about 13, from about 12.5 to about 15, from about 12.5 to about14.5, from about 12.5 to about 14, from about 12.5 to about 13.5, fromabout 12.5 to about 13, from about 13 to about 15, from about 13 toabout 14.5, from about 13 to about 14, from about 13 to about 13.5, fromabout 13.5 to about 15, from about 13.5 to about 14.5, from about 13.5to about 14, from about 14 to about 15, from about 14 to about 14.5, andfrom about 14.5 to about 15.

In a particular embodiment comprising a base, the pH can be from about 9to about 15, from about 9 to about 14 or from about 8 to about 14.

Exemplary bases can include, but are not limited to, sodium hydroxide,potassium hydroxide, lithium hydroxide, pyridine, pyrrole, piperazine,pyrrolidine, piperidine, picoline, monoethanolamine, diethanolamine,dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine,diazabicyclooctane, diazabicyclononane, diazabicycloundecene,tetramethylammonium hydroxide, tetraethylammonium hydroxide,tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, ammonia,ammonium hydroxide, methylamine, ethylamine, propylamine, butylamine,pentylamine, hexylamine, octylamine, nonylamine, decylamine,N,N-dimethylamine, N,N-diethylamine, N,N-dipropylamine,N,N-dibutylamine, trimethylamine, triethylamine, tripropylamine,tributylamine, cyclohexylamine, trimethylimidine,1-amino-3-methylbutane, dimethylglycine, 3-amino-3-methylamine, and thelike. These bases may be used either singly or in combination. In aparticular embodiment, the base can comprise or be sodium hydroxideand/or ammonium hydroxide.

In certain embodiments where the aqueous mixture comprises an acid, theaqueous mixture can have a pH from about 0.1 to about 6.0, about 0.1 toabout 5.5, about 0.1 to about 5.0, from about 0.1 to about 4.8, fromabout 0.1 to about 4.5, from about 0.1 to about 4.2, from about 0.1 toabout 4.0, from about 0.1 to about 3.8, from about 0.1 to about 3.5,from about 0.1 to about 3.2, from about 0.1 to about 3.0, from about 0.1to about 2.8, from about 0.1 to about 2.5, from about 0.1 to about 2.2,from about 0.1 to about 2.0, from about 0.1 to about 1.8, from about 0.1to about 1.5, from about 0.1 to about 1.2, from about 0.1 to about 1.0,from about 0.1 to about 0.8, from about 0.1 to about 0.5, from about 0.1to about 0.2, about 0.2 to about 6.0, about 0.2 to about 5.5, from about0.2 to about 5, from about 0.2 to about 4.8, from about 0.2 to about4.5, from about 0.2 to about 4.2, from about 0.2 to about 4.0, fromabout 0.2 to about 3.8, from about 0.2 to about 3.5, from about 0.2 toabout 3.2, from about 0.2 to about 3.0, from about 0.2 to about 2.8,from about 0.2 to about 2.5, from about 0.2 to about 2.2, from about 0.2to about 2.0, from about 0.2 to about 1.8, from about 0.2 to about 1.5,from about 0.2 to about 1.2, from about 0.2 to about 1.0, from about 0.2to about 0.8, from about 0.2 to about 0.5, about 0.5 to about 6.0, about0.5 to about 5.5, from about 0.5 to about 5, from about 0.5 to about4.8, from about 0.5 to about 4.5, from about 0.5 to about 4.2, fromabout 0.5 to about 4.0, from about 0.5 to about 3.8, from about 0.5 toabout 3.5, from about 0.5 to about 3.2, from about 0.5 to about 3.0,from about 0.5 to about 2.8, from about 0.5 to about 2.5, from about 0.5to about 2.2, from about 0.5 to about 2.0, from about 0.5 to about 1.8,from about 0.5 to about 1.5, from about 0.5 to about 1.2, from about 0.5to about 1.0, from about 0.5 to about 0.8, about 0.8 to about 6.0, about0.8 to about 5.5, from about 0.8 to about 5, from about 0.8 to about4.8, from about 0.8 to about 4.5, from about 0.8 to about 4.2, fromabout 0.8 to about 4.0, from about 0.8 to about 3.8, from about 0.8 toabout 3.5, from about 0.8 to about 3.2, from about 0.8 to about 3.0,from about 0.8 to about 2.8, from about 0.8 to about 2.5, from about 0.8to about 2.2, from about 0.8 to about 2.0, from about 0.8 to about 1.8,from about 0.8 to about 1.5, from about 0.8 to about 1.2, from about 0.8to about 1.0, about 1.0 to about 6.0, about 1.0 to about 5.5, from about1.0 to about 5.0, from about 1.0 to about 4.8, from about 1.0 to about4.5, from about 1.0 to about 4.2, from about 1.0 to about 4.0, fromabout 1.0 to about 3.8, from about 1.0 to about 3.5, from about 1.0 toabout 3.2, from about 1.0 to about 3.0, from about 1.0 to about 2.8,from about 1.0 to about 2.5, from about 1.0 to about 2.2, from about 1.0to about 2.0, from about 1.0 to about 1.8, from about 1.0 to about 1.5,from about 1.0 to about 1.2, about 1.2 to about 6.0, about 1.2 to about5.5, from about 1.2 to about 5.0, from about 1.2 to about 4.8, fromabout 1.2 to about 4.5, from about 1.2 to about 4.2, from about 1.2 toabout 4.0, from about 1.2 to about 3.8, from about 1.2 to about 3.5,from about 1.2 to about 3.2, from about 1.2 to about 3.0, from about 1.2to about 2.8, from about 1.2 to about 2.5, from about 1.2 to about 2.2,from about 1.2 to about 2.0, from about 1.2 to about 1.8, from about 1.2to about 1.5, about 1.5 to about 6.0, about 1.5 to about 5.5, from about1.5 to about 5.0, from about 1.5 to about 4.8, from about 1.5 to about4.5, from about 1.5 to about 4.2, from about 1.5 to about 4.0, fromabout 1.5 to about 3.8, from about 1.5 to about 3.5, from about 1.5 toabout 3.2, from about 1.5 to about 3.0, from about 1.5 to about 2.8,from about 1.5 to about 2.5, from about 1.5 to about 2.2, from about 1.5to about 2.0, from about 1.5 to about 1.8, about 1.8 to about 6.0, about1.8 to about 5.5, from about 1.8 to about 5.0, from about 1.8 to about4.8, from about 1.8 to about 4.5, from about 1.8 to about 4.2, fromabout 1.8 to about 4.0, from about 1.8 to about 3.8, from about 1.8 toabout 3.5, from about 1.8 to about 3.2, from about 1.8 to about 3.0,from about 1.8 to about 2.8, from about 1.8 to about 2.5, from about 1.8to about 2.2, from about 1.8 to about 2.0, about 2.0 to about 6.0, about2.0 to about 5.5, from about 2.0 to about 5.0, from about 2.0 to about4.8, from about 2.0 to about 4.5, from about 2.0 to about 4.2, fromabout 2.0 to about 4.0, from about 2.0 to about 3.8, from about 2.0 toabout 3.5, from about 2.0 to about 3.2, from about 2.0 to about 3.0,from about 2.0 to about 2.8, from about 2.0 to about 2.5, from about 2.0to about 2.2, about 2.2 to about 6.0, about 2.2 to about 5.5, from about2.2 to about 5.0, from about 2.2 to about 4.8, from about 2.2 to about4.5, from about 2.2 to about 4.2, from about 2.2 to about 4.0, fromabout 2.2 to about 3.8, from about 2.2 to about 3.5, from about 2.2 toabout 3.2, from about 2.2 to about 3.0, from about 2.2 to about 2.8,from about 2.2 to about 2.5, about 2.5 to about 6.0, about 2.5 to about5.5, from about 2.5 to about 5.0, from about 2.5 to about 4.8, fromabout 2.5 to about 4.5, from about 2.5 to about 4.2, from about 2.5 toabout 4.0, from about 2.5 to about 3.8, from about 2.5 to about 3.5,from about 2.5 to about 3.2, from about 2.5 to about 3.0, from about 2.5to about 2.8, from about 2.8 to about 6.0, about 2.8 to about 5.5, fromabout 2.8 to about 5.0, from about 2.8 to about 4.8, from about 2.8 toabout 4.5, from about 2.8 to about 4.2, from about 2.8 to about 4.0,from about 2.8 to about 3.8, from about 2.8 to about 3.5, from about 2.8to about 3.2, from about 2.8 to about 3.0, from about 3.0 to about 6.0,from about 3.5 to about 5.5, from about 3.0 to about 5.0, from about 3.0to about 4.8, from about 3.0 to about 4.5, from about 3.0 to about 4.2,from about 3.0 to about 4.0, from about 3.0 to about 3.8, from about 3.0to about 3.5, from about 3.0 to about 3.2, from about 3.2 to about 6.0,from about 3.2 to about 5.5, from about 3.2 to about 5, from about 3.2to about 4.8, from about 3.2 to about 4.5, from about 3.2 to about 4.2,from about 3.2 to about 4.0, from about 3.2 to about 3.8, from about 3.2to about 3.5, from about 3.5 to about 6.0, from about 3.5 to about 5.5,from about 3.5 to about 5, from about 3.5 to about 4.8, from about 3.5to about 4.5, from about 3.5 to about 4.2, from about 3.5 to about 4.0,from about 3.5 to about 3.8, from about 3.8 to about 5, from about 3.8to about 4.8, from about 3.8 to about 4.5, from about 3.8 to about 4.2,from about 3.8 to about 4.0, from about 4.0 to about 6.0, from about 4.0to about 5.5, from about 4.0 to about 5, from about 4.0 to about 4.8,from about 4.0 to about 4.5, from about 4.0 to about 4.2, from about 4.2to about 5, from about 4.2 to about 4.8, from about 4.2 to about 4.5,from about 4.5 to about 5, from about 4.5 to about 4.8, or from about4.8 to about 5.

In a particular embodiment comprising an acid, the pH can be from about0.01 to about 6.0, about 0.2 to about 6.0, about 0.2 to about 5.0 orabout 0.2 to about 4.5.

Exemplary acids can include, but are not limited to, inorganic acidssuch as hydrochloric acid, nitric acid, sulfuric acid, hydrofluoricacid, phosphoric acid, boric acid and oxalic acid; and organic acidssuch as acetic acid, propionic acid, butanoic acid, pentanoic acid,hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoicacid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacicacid, gallic acid, butyric acid, mellitic acid, arachidonic acid,shikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleicacid, linolenic acid, salicylic acid, benzoic acid, p-amino-benzoicacid, p-toluenesulfonic acid, benzenesulfonic acid, monochloroaceticacid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid,formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid,citric acid, tartaric acid, succinic acid, itaconic acid, mesaconicacid, citraconic acid, malic acid, a hydrolysate of glutaric acid, ahydrolysate of maleic anhydride, a hydrolysate of phthalic anhydride,and the like. These acids may be used either singly or in combination.In a particular embodiment, the acid can comprise or be hydrochloricacid.

III.B. Compounds of Formula (Ia)

The methods provided herein comprise the step of adding at least onecyclic compound of Formula

into the aqueous mixture to form a solution, wherein each R³independently can be a X¹OX²X³SiX⁴ group, wherein each X¹ can be a C₁-C₄alkyl group; each X² and X³ independently can be a C₁-C₄ alkyl group ora C₁-C₄ alkoxy group; and each X⁴ can be a C₁-C₈ alkylene group bondedto a nitrogen atom of the cyclic compound

In various embodiments, each X¹ canbe a C₁-C₄ alkyl, a C₁-C₃ alkyl, aC₁-C₂ alkyl or methyl.

Additionally or alternatively, each X² and X³ independently can be aC₁-C₄ alkyl group, a C₁-C₃ alkyl group, a C₁-C₂ alkyl group or methyl.

Additionally or alternatively, each X² and X³ independently can be aC₁-C₄ alkoxy group, a C₁-C₃ alkoxy group, a C₁-C₂ alkoxy group ormethoxy.

Additionally or alternatively, each X² and X³ independently can be aC₁-C₂ alkyl group or a C₁-C₂ alkoxy group.

Additionally or alternatively, each X¹ can be C₁-C₂ alkyl group; andeach X² and X³ independently can be a C₁-C₂ alkyl group or a C₁-C₂alkoxy group.

Additionally or alternatively, each X⁴ can be a C₁-C₇ alkylene groupbonded to a nitrogen atom of the cyclic compound, a C₁-C₇ alkylene groupbonded to a nitrogen atom of the cyclic compound, a C₁-C₆ alkylene groupbonded to a nitrogen atom of the cyclic compound, a C₁-C₄ alkylene groupbonded to a nitrogen atom of the cyclic compound, a C₁-C₃ alkylene groupbonded to a nitrogen atom of the cyclic compound, a C₁-C₂ alkylene groupbonded to a nitrogen atom of the cyclic compound, or —CH₂— bonded to anitrogen atom of the cyclic compound.

Additionally or alternatively, each X¹ can be a C₁-C₂ alkyl group; eachX² and X³ independently can be a C₁-C₂ alkyl group or a C₁-C₂ alkoxygroup; and each X⁴ can be a C₁-C₄ alkylene group bonded to a nitrogenatom of the cyclic compound.

In a particular embodiment, each X¹ can be methyl; each X² and X³independently can be methoxy; and each X⁴ can be —CH₂CH₂CH₂—, such thatthe compound corresponding to Formula (Ia) can betris(3-trimethoxysilylpropyl)-isocyanurate.

As mentioned hereinabove, the at least one compound of Formula (Ia) canadditionally or alternatively be at least partially hydroxylated and/orpolymerized/oligomerized when added into the aqueous mixture to form asolution.

III.C. Compounds of Formula (IIa)

In additional embodiments, the methods provided herein can compriseadding to the aqueous solution a compound of formula [X⁵OX⁶SiCH₂]₃(IIa), to obtain an organosilica material which is a copolymercomprising at least one independent unit of Formula (I) as describedherein and at least one independent unit of Formula (II) as describedherein, wherein each X⁵ represents a C₁-C₄ alkyl group and each X⁶represents a C₁-C₄ alkyl group or a C₁-C₄ alkoxy group.

In various embodiments, each X⁵ can be a C₁-C₄ alkyl group, a C₁-C₃alkyl group, a C₁-C₂ alkyl group or methyl.

Additionally or alternatively, each X⁶ can be a C₁-C₄ alkyl group, aC₁-C₃ alkyl group, a C₁-C₂ alkyl group or methyl.

Additionally or alternatively, each X⁶ can be a C₁-C₄ alkoxy group, aC₁-C₃ alkoxy group, a C₁-C₂ alkoxy group or methoxy.

Additionally or alternatively, each X⁶ can be a C₁-C₂ alkyl group or aC₁-C₂ alkoxy group.

Additionally or alternatively, each X⁵ can be a C₁-C₂ alkyl group andeach X⁶ can be a C₁-C₂ alkyl group or a C₁-C₂ alkoxy group.

In a particular embodiment, each X⁵ can be ethyl and each X⁶ can beethoxy, such that the compound corresponding to Formula (IIa) can be1,1,3,3,5,5-hexaethoxy-1,3,5-trisilacyclohexane, ([(EtO)₂SiCH₂]₃).

In a particular embodiment, each X⁵ can be ethyl and each X⁶ can bemethyl, such that compound corresponding to Formula (IIa) can be1,3,5-trimethyl-1,3,5-triethoxy-1,3,5-trisilacyclohexane,([EtOCH₃SiCH₂]₃).

In another particular embodiment,tris(3-trimethoxysilylpropyl)isocyanurate and1,1,3,3,5,5-hexaethoxy-1,3,5-trisalacyclohexane can be added to aqueousmixture to obtain an organosilica material with is copolymer comprisingindependent units of Formula (I) and independent units of Formula (II).

When more than one compound of Formula (IIa) is used, the respectivecompounds may be used in a wide variety of molar ratios. For example, iftwo compounds of Formula (IIa) are used, the molar ratio of eachcompound may vary from 1:99 to 99:1, such as from 10:90 to 90:10. Theuse of different compounds of Formula (IIa) allows to tailor theproperties of the organosilica materials made by the process of theinvention, as will be further explained in the examples and in thesection of this specification describing the properties of theorganosilicas made by the present processes.

III.D. Compounds of Formula (IIIa)

In additional embodiments, the methods provided herein can furthercomprise adding to the aqueous solution a compound of FormulaX⁷OX⁸X⁹X¹⁰Si (IIIa) to obtain an organosilica material which is acopolymer comprising at least one independent unit of Formula (I) asdescribed herein, optionally at least one independent unit of Formula(II) as described herein and at least one independent unit of Formula(III) as described herein, wherein each X⁷ can be a C₁-C₆ alkyl group;and X⁸, X⁹ and X¹⁰ each independently can be selected from the groupconsisting of a C₁-C₆ alkyl group, a C₁-C₆ alkoxy group, anitrogen-containing C₁-C₁₀ alkyl group, a nitrogen-containingheteroaralkyl group, and a nitrogen-containing optionally substitutedheterocycloalkyl group.

In one embodiment, each X⁷ can be a C₁-C₅ alkyl group, a C₁-C₄ alkylgroup, a C₁-C₃ alkyl group, a C₁-C₂ alkyl group, or methyl. Inparticular, each X⁷ can be methyl or ethyl.

Additionally or alternatively, X⁸, X⁹ and X¹⁰ can be each independentlya C₁-C₅ alkyl group, a C₁-C₄ alkyl group, a C₁-C₃ alkyl group, a C₁-C₂alkyl group, or methyl.

Additionally or alternatively, each X⁷ can be a C₁-C₂ alkyl group andX⁸, X⁹ and X¹⁰ can be each independently a C₁-C₂ alkyl group.

Additionally or alternatively, X⁸, X⁹ and X¹⁰ can be each independentlya C₁-C₅ alkoxy group, a C₁-C₄ alkoxy group, a C₁-C₃ alkoxy group, aC₁-C₂ alkoxy group, or methoxy.

Additionally or alternatively, each X⁷ can be a C₁-C₂ alkyl group andX⁸, X⁹ and X¹⁰ can be each independently a C₁₀-C₂ alkoxy group.

Additionally or alternatively, each X⁷ can be a C₁-C₂ alkyl group andX⁸, X⁹ and X¹⁰ can be each independently a C₁-C₂ alkyl group or a C₁-C₂alkoxy group.

Additionally or alternatively, X⁸, X⁹ and X¹⁰ can be each independentlya nitrogen-containing C₁-C₉ alkyl group, a nitrogen-containing C₁-C₈alkyl group, a nitrogen-containing C₁-C₇ alkyl group, anitrogen-containing C₁-C₆ alkyl group, a nitrogen-containing C₁-C₅ alkylgroup, a nitrogen-containing C₁-C₄ alkyl group, a nitrogen-containingC₁-C₃ alkyl group, a nitrogen-containing C₁-C₂ alkyl group, or amethylamine. In particular, X⁸, X⁹ and X¹⁰ can be each independently anitrogen-containing C₂-C₁₀ alkyl group, a nitrogen-containing C₃-C₁₀alkyl group, a nitrogen-containing C₃-C₉ alkyl group, or anitrogen-containing C₃-C₈ alkyl group. The aforementionednitrogen-containing alkyl groups may have one or more nitrogen atoms(e.g., 2, 3, etc.). Examples of nitrogen-containing C₁-C₁₀ alkyl groupsinclude, but are not limited to,

Additionally or alternatively, each X⁷ can be a C₁-C₂ alkyl group andX⁸, X⁹ and X¹⁰ can be each independently a nitrogen-containing C₃-C₈alkyl group.

Additionally or alternatively, each X⁷ can be a C₁-C₂ alkyl group andX⁸, X⁹ and X¹⁰ can be each independently a C₁-C₂ alkyl group, a C₁-C₂alkoxy group or a nitrogen-containing C₃-C₈ alkyl group.

Additionally or alternatively, X⁸, X⁹ and X¹⁰ can be each independentlya nitrogen-containing heteroaralkyl group. The nitrogen-containingheteroaralkyl group can be a nitrogen-containing C₄-C₁₂ heteroaralkylgroup, a nitrogen-containing C₄-C₁₀ heteroaralkyl group, or anitrogen-containing C₄-C₈ heteroaralkyl group. Examples ofnitrogen-containing heteroaralkyl groups include but are not limited topyridinylethyl, pyridinylpropyl, pyridinylmethyl, indolylmethyl,pyrazinylethyl, and pyrazinylpropyl. The aforementionednitrogen-containing heteroaralkyl groups may have one or more nitrogenatoms (e.g., 2, 3, etc.).

Additionally or alternatively, each X⁷ can be a C₁-C₂ alkyl group andX⁸, X⁹ and X¹⁰ can be each independently a nitrogen-containingheteroaralkyl group.

Additionally or alternatively, each X⁷ can be a C₁-C₂ alkyl group andX⁸, X⁹ and X¹⁰ can be each independently a C₁-C₂ alkyl group, a C₁-C₂alkoxy group, a nitrogen-containing C₃-C₈ alkyl group or anitrogen-containing heteroaralkyl group.

Additionally or alternatively, X⁸, X⁹ and X¹⁰ can be each independentlya nitrogen-containing heterocycloalkyl group, wherein theheterocycloalkyl group may be optionally substituted with a C₁-C₆ alkylgroup, particularly a C₁-C₄ alkyl group. The nitrogen-containingheterocycloalkyl group can be a nitrogen-containing C₄-C₁₂heterocycloalkyl group, a nitrogen-containing C₄-C₁₀ heterocycloalkylgroup, or a nitrogen-containing C₄-C₈ heterocycloalkyl group. Examplesof nitrogen-containing heterocycloalkyl groups include but are notlimited to piperazinylethyl, piperazinylpropyl, piperidinylethyl,piperidinylpropyl. The aforementioned nitrogen-containingheterocycloalkyl groups may have one or more nitrogen atoms (e.g., 2, 3,etc.).

Additionally or alternatively, each X⁷ can be a C₁-C₂ alkyl group andR⁴, R⁵ and R⁶ can be each independently a nitrogen-containing optionallysubstituted heterocycloalkyl group.

Additionally or alternatively, each R³ can be a C₁-C₂ alkyl group andX⁸, X⁹ and X¹⁰ can be each independently a C₁-C₂ alkyl group, a C₁-C₂alkoxy group, a nitrogen-containing C₃-C₈ alkyl group, anitrogen-containing heteroaralkyl group, or a nitrogen-containingoptionally substituted heterocycloalkyl group.

Additionally or alternatively, each X⁷ can be a C₁-C₂ alkyl group andX⁸, X⁹ and X¹⁰ can be each independently a C₁-C₂ alkyl group, C₁-C₂alkoxy group, a nitrogen-containing C₃-C₁₀ alkyl group, anitrogen-containing C₄-C₁₀ heteroaralkyl group, or a nitrogen-containingoptionally substituted C₄-C₁₀ heterocycloalkyl group.

In a particular embodiment, each X⁷ can be ethyl and X⁸, X⁹ and X¹⁰ canbe ethoxy, such that the compound corresponding to Formula (IIa) can betetraethyl orthosilicate (TEOS) ((EtO)₄Si).

In another particular embodiment,tris(3-trimethoxysilylpropyl)isocyanurate and tetraethyl orthosilicate(TEOS) ((EtO)₄Si) can be added to the aqueous mixture to obtain anorganosilica material with is copolymer comprising units of Formula (I)and units of Formula (III).

In another particular embodiment, each X⁷ can be ethyl, X⁸ can be methyland X⁹ and X¹⁰ can be ethoxy, such that the compound corresponding toFormula (IIa) can be methyltriethoxysilane (MTES) ((EtO)₃CH₃Si).

In another particular embodiment, a compound of Formula (Ia) can betris(3-trimethoxysilylpropyl)isocyanurate and a compound of Formula(IIa) can be methyltriethoxysilane (MTES) ((EtO)₃CH₃Si).

In another particular embodiment, each X⁷ can be ethyl, X⁸ and X⁹ can beethoxy and each X^(m) can be

such that the compound corresponding to Formula (IIa) can be(3-aminopropyl)triethoxysilane(H₂N(CH₂)₃(EtO)₃Si).

In another particular embodiment, a compound of Formula (Ia) can betris(3-trimethoxysilylpropyl)isocyanurate and a compound of Formula(IIa) can be (3-aminopropyl)triethoxysilane(H₂N(CH₂)₃(EtO)₃Si).

In another particular embodiment, each X⁷ can be methyl, X⁸ and X⁹ eachcan be methoxy and each X¹⁰ can be

such that the compound corresponding to Formula (IIIa) can be(N,N-dimethylaminopropyl)trimethoxysilane(((CH₃)₂N(CH₂)₃)(MeO)₃Si).

In another particular embodiment, a compound of Formula (Ia) can betris(3-trimethoxysilylpropyl)isocyanurate and a compound of Formula(IIa) can be(N,N-dimethylaminopropyl)trimethoxysilane(((CH₃)₂N(CH₂)₃)(MeO)₃Si).

In another particular embodiment, each X⁷ can be ethyl, each X⁸ and X⁹can be ethoxy and X¹⁰ can be

such that the compound corresponding to Formula (IIIa) can be(N-(2-aminoethyl)-3-aminopropyltriethoxysilane((H₂N(CH₂)₂NH(CH₂)₃)(EtO)₂Si).

In another particular embodiment, a compound of Formula (Ia) can betris(3-trimethoxysilylpropyl)isocyanurate and Formula a compound of(IIa) can be (N-(2-aminoethyl)-3-aminopropyltriethoxysilane((H₂N(CH₂)₂NH(CH₂)₃)(EtO)₂Si).

In another particular embodiment, each X⁷ can be ethyl, each X⁸ and X⁹can be ethoxy and X¹⁰ can be

such that the compound corresponding to Formula (IIa) can be4-methyl-1-(3-triethoxysilylpropyl)-piperazine.

In another particular embodiment, a compound of Formula (Ia) can betris(3-trimethoxysilylpropyl)isocyanurate and a compound of Formula(IIIa) can be 4-methyl-1-(3-triethoxysilylpropyl)-piperazine.

In another particular embodiment, each X⁷ can be ethyl, each X⁸ and X⁹can be ethoxy and X¹⁰ can be

such that the compound corresponding to Formula (IIIa) can be4-(2-(triethoxysily)ethyl)pyridine.

In another particular embodiment, a compound of Formula (Ia) can betris(3-trimethoxysilylpropyl)isocyanurate and a compound of Formula(IIa) can be 4-(2-(triethoxysily)ethyl)pyridine.

In another particular embodiment, each X⁷ can be ethyl, each X⁸ and X⁹can be ethoxy and X¹⁰ can be

such that the compound corresponding to Formula (IIIa) can be1-(3-(triethoxysilyl)propyl)-4,5-dihydro-1H-imidazole.

In another particular embodiment, a compound of Formula (Ia) can betris(3-trimethoxysilylpropyl)isocyanurate and a compound of Formula(IIIa) can be 1-(3-(triethoxysilyl)propyl)-4,5-dihydro-1H-imidazole.

Additionally or alternatively, the compound of Formula (IIIa) isselected from the group consisting of tetraethyl orthosilicate ormethyltriethoxysilane, (N,N-dimethylaminopropyl)trimethoxysilane,N-(2-aminoethyl)-3-aminopropyltriethoxysilane,4-methyl-1-(3-triethoxysilylpropyl)-piperazine,4-(2-(triethoxysily)ethyl)pyridine, 1-(3-(triethoxysilyl)propyl)-4,5-dihydro-1H-imidazole, and (3-aminopropyl)triethoxysilane.

The molar ratio of compound of Formula (Ia) to compound of Formula(IIIa) may vary within wide limits, such as from about 99:1 to about1:99, from about 1:5 to about 5:1, from about 4:1 to about 1:4 or fromabout 3:2 to about 2:3. For example, a molar ratio of compound ofFormula (Ia) to compound of Formula (IIIa) can be from about 4:1 to 1:4or from about 2.5:1 to about 1:2.5, about 2:1 to about 1:2, such asabout 1.5:1 to about 1.5:1.

III.E. Compounds of Formula (IVa)

In additional embodiments, the methods provided herein can furthercomprise adding to the aqueous solution a compound of FormulaX¹¹X¹²X¹³Si—R⁴—SiX¹¹X¹²X¹³ (IVa) to obtain an organosilica materialwhich is a copolymer comprising at at least one independent unit Formula(I) as described herein, optionally at least one independent unit ofFormula (II) as described herein, optionally at least one independentunit of Formula (III) as described herein and at least one independentunit of Formula (IV) as described herein, wherein each X¹¹ independentlyrepresents a C₁-C₄ alkoxy group; each X¹² and X¹³ independentlyrepresent a C₁-C₄ alkoxy group or a C₁-C₄ alkyl group; and each R⁴ isselected from the group consisting a C₁-C₈ alkylene group, a C₂-C₈alkenylene group, a C₂-C₈ alkynylene group, a nitrogen-containing C₁-C₁₀alkylene group, an optionally substituted C₆-C₂₀ aralkyl and anoptionally substituted C₄-C₂₀ heterocycloalkyl group.

In one embodiment, each X¹¹ can be a C₁-C₃ alkoxy group, a C₁-C₂ alkoxygroup, or methoxy.

Additionally or alternatively, each X¹² and X¹³ independently can be aC₁-C₃ alkoxy group, a C₁-C₂ alkoxy group, or methoxy.

Additionally or alternatively, each X¹¹ can be a C₁-C₂ alkoxy group andeach X¹² and X¹³ independently can be a C₁-C₂ alkoxy group.

Additionally or alternatively, each X¹² and X¹³ independently can be aC₁-C₄ alkyl group, a C₁-C₃ alkyl group, a C₁-C₂ alkyl group, or methyl.

Additionally or alternatively, each X¹¹can be a C₁-C₂ alkoxy group and aC₁-C₃ alkyl group each independently can be a C₁-C₂ alkyl group.

Additionally or alternatively, each X¹¹can be a C₁-C₂ alkoxy group andeach X¹² and X¹³ independently can be a C₁-C₂ alkoxy group or a C₁-C₂alkyl group.

Additionally or alternatively, each R⁴ can be a C₁-C₇ alkylene group, aC₁-C₆ alkylene group, a C₁-C₅ alkylene group, a C₁-C₄ alkylene group, aC₁-C₃ alkylene group, a C₁-C₂ alkylene group, or —CH₂—.

Additionally or alternatively, each X¹¹ can be a C₁-C₂ alkoxy group;each X¹² and X¹³ independently can be a C₁-C₂ alkoxy group or a C₁-C₂alkyl group; and each R⁴ can be a C₁-C₄ alkylene group.

Additionally or alternatively, each R⁴ can be a C₂-C₇ alkenylene group,a C₁-C₆ alkenylene group, a C₂-C₅ alkenylene group, a C₂-C₄ a alkenylenegroup, a C₂-C₃ alkenylene group, or —CH═CH—.

Additionally or alternatively, each X¹¹ can be a C₁-C₂ alkoxy group;each X¹² and X¹³ independently can be a C₁-C₂ alkoxy group or a C₁-C₂alkyl group; and each R⁴ can be a C₂-C₄ alkenylene group.

Additionally or alternatively, each X¹¹ can be a C₁-C₂ alkoxy group;each X¹² and X¹³ independently can be a C₁-C₂ alkoxy group or a C₁-C₂alkyl group; and each R⁴ can be a C₁-C₄ alkylene group or a C₂-C₄alkenylene group.

Additionally or alternatively, each R⁴ can be a C₂-C₇ alkynylene group,a C₁-C₆ alkynylene group, a C₂-C₅ alkynylene group, a C₂-C₄ a alkynylenegroup, a C₂-C₃ alkynylene group, or —C≡C—.

Additionally or alternatively, each X¹¹ can be a C₁-C₂ alkoxy group;each X¹² and X¹³ independently can be a C₁-C₂ alkoxy group or a C₁-C₂alkyl group; and each R⁴ can be a C₂-C₄ alkynylene group.

Additionally or alternatively, each X¹¹ can be a C₁-C₂ alkoxy group;each X¹² and X¹³ independently can be a C₁-C₂ alkoxy group or a C₁-C₂alkyl group; and each R⁴ can be a C₁-C₄ alkylene group, a C₂-C₄alkenylene group or a C₂-C₄ alkynylene group.

Additionally or alternatively, each R⁴ can be a nitrogen-containingC₂-C₁₀ alkylene group, a nitrogen-containing C₃-C₁₀ alkylene group, anitrogen-containing C₄-C₁₀ alkylene group, a nitrogen-containing C₄-C₉alkylene group, a nitrogen-containing C₄-C₈ alkylene group, or nitrogencontaining C₃-C₈ alkylene group. The aforementioned nitrogen-containingalkylene groups may have one or more nitrogen atoms (e.g., 2, 3, etc.).Examples of nitrogen-containing alkylene groups include, but are notlimited to,

Additionally or alternatively, each X¹¹ can be a C₁-C₂ alkoxy group;each X¹² and X¹³ independently can be a C₁-C₂ alkoxy group or a C₁-C₂alkyl group; and each R⁴ can be a nitrogen-containing C₄-C₁₀ alkylenegroup.

Additionally or alternatively, each X¹¹ can be a C₁-C₂ alkoxy group;each X¹² and X¹³ independently can be a C₁-C₂ alkoxy group or a C₁-C₂alkyl group; and each R⁴ can be a C₁-C₄ alkylene group, a C₂-C₄alkenylene group, a C₂-C₄ alkynylene group or a nitrogen-containingC₄-C₁₀ alkylene group.

Additionally or alternatively, each R⁴ can be an optionally substitutedC₆-C₂₀ aralkyl, an optionally substituted C₆-C₁₄ aralkyl, or anoptionally substituted C₆-C₁₀ aralkyl. Examples of C₆-C₂₀ aralkylsinclude, but are not limited to, phenylmethyl, phenylethyl, andnaphthylmethyl. The aralkyl may be optionally substituted with a C₁-C₆alkyl group, particularly a C₁-C₄ alkyl group.

Additionally or alternatively, each X¹¹ can be a C₁-C₂ alkoxy group;each X¹² and X¹³ independently can be a C₁-C₂ alkoxy group or a C₁-C₂alkyl group; and each R⁴ can be an optionally substituted C₆-C₁₀aralkyl.

Additionally or alternatively, each X¹¹ can be a C₁-C₂ alkoxy group;each X¹² and X¹³ independently can be a C₁-C₂ alkoxy group or a C₁-C₂alkyl group; and each R⁴ can be a C₁-C₄ alkylene group, a C₂-C₄alkenylene group, a C₂-C₄ alkynylene group, or an optionally substitutedC₆-C₁₀ aralkyl.

Additionally or alternatively, each R⁴ can be an optionally substitutedC₄-C₂₀ heterocycloalkyl group, an optionally substituted C₄-C₁₆heterocycloalkyl group, an optionally substituted C₄-C₁₂heterocycloalkyl group, or an optionally substituted C₄-C₁₀heterocycloalkyl group. Examples of C₄-C₂₀ heterocycloalkyl groupsinclude, but are not limited to, thienylmethyl, furylethyl,pyrrolylmethyl, piperazinylethyl, pyridylmethyl, benzoxazolylethyl,quinolinylpropyl, and imidazolylpropyl. The heterocycloalkyl may beoptionally substituted with a C₁-C₆ alkyl group, particularly a C₁-C₄alkyl group.

Additionally or alternatively, each X¹¹can be a C₁-C₂ alkoxy group; eachX¹² and X¹³ independently can be a C₁-C₂ alkoxy group or a C₁-C₂ alkylgroup; and each R⁴ can be an optionally substituted C₄-C₁₂heterocycloalkyl group.

Additionally or alternatively, each X¹¹ can be a C₁-C₂ alkoxy group;each X¹² and X¹³ independently can be a C₁-C₂ alkoxy group or a C₁-C₂alkyl group; and each R⁴ can be a C₁-C₄ alkylene group, a C₂-C₄alkenylene group, a C₂-C₄ alkynylene group, an optionally substitutedC₆-C₁₀ aralkyl, or an optionally substituted C₄-C₁₂ heterocycloalkylgroup.

In a particular embodiment, each X¹¹ and X¹² can be ethoxy, each X¹³ canbe methyl and each R⁴ can be —CH₂CH₂—, such that compound correspondingto Formula (IVa) can be1,2-bis(methyldiethoxysilyl)ethane(CH₃(EtO)₂Si—CH₂CH₂—Si(EtO)₂CH₃).

In another particular embodiment, a compound of Formula (Ia) can betris(3-trimethoxysilylpropyl)isocyanurate and a compound of Formula(IVa) can be1,2-bis(methyldiethoxysilyl)ethane(CH₃(EtO)₂Si—CH₂CH₂—Si(EtO)₂CH₃).

In another particular embodiment, each X¹¹, X¹² and X¹³ can be ethoxyand each R⁴ can be —CH₂—, such that compound corresponding to Formula(IVa) can be bis(triethoxysilyl)methane((EtO)₃Si—CH₂—Si(EtO)₃).

In another particular embodiment, a compound of Formula (Ia) can betris(3-trimethoxysilylpropyl)isocyanurate and a compound of Formula(IVa) can be bis(triethoxysilyl)methane((EtO)₃Si—CH₂—Si(EtO)₃).

In another particular embodiment, each X¹¹, X¹² and X¹³ can be ethoxyand each R⁴ can be —HC═CH—, such that compound corresponding to Formula(IVa) can be 1,2-bis(triethoxysilyl)ethylene((EtO)₃Si—HC═CH—Si(EtO)₃).

In another particular embodiment, a compound of Formula (Ia) can betris(3-trimethoxysilylpropyl)isocyanurate and a compound of Formula(IVa) can be 1,2-bis(triethoxysilyl)ethylene((EtO)₃Si—HC═CH—Si(EtO)₃).

In a particular embodiment, each X¹¹, X¹² and X¹³ can be methoxy andeach R⁴ can be

such that compound corresponding to Formula (IVa) can beN,N′-bis[(3-trimethoxysilyl)propyl]ethylenediamine.

In another particular embodiment, a compound of Formula (Ia) can betris(3-trimethoxysilylpropyl)isocyanurate and a compound of Formula(IVa) can be N,N′-bis[(3-trimethoxysilyl)propyl]ethylenediamine.

In another particular embodiment, each X¹¹ and X¹² can be ethoxy, X¹³can be methyl and each R⁴ can be

such that compound corresponding to Formula (IVa) can bebis[(methyldiethoxysilyl)propyl]amine.

In another particular embodiment, a compound of Formula (Ia) can betris(3-trimethoxysilylpropyl)isocyanurate and a compound of Formula(IVa) can be bis[(methyldiethoxysilyl)propyl]amine.

In another particular embodiment, each X¹¹ and X¹² can be methoxy, eachX¹³ can be methyl and each R⁴ can be

such that compound corresponding to Formula (IVa) can bebis[(methyldimethoxysilyl)propyl]-N-methylamine.

In another particular embodiment, Formula (Ia) can betris(3-trimethoxysilylpropyl)isocyanurate and Formula (IVa) can bebis[(methyldimethoxysilyl)propyl]-N-methylamine.

The molar ratio of compound of Formula (Ia) to compound of Formula (IVa)may vary within wide limits, such as from about 99:1 to about 1:99, fromabout 1:5 to about 5:1, from about 4:1 to about 1:4 or from about 3:2 toabout 2:3. For example, a molar ratio of compound of Formula (Ia) tocompound of Formula (IVa) can be from about 4:1 to 1:4 or from about2.5:1 to 1:2.5, about 2:1 to about 1:2, such as about 1.5:1 to about1.5:1.

III.F. Sources of Trivalent Metal Oxides

In additional embodiments, the methods provided herein can compriseadding to the aqueous solution a source of a trivalent metal oxide.

Sources of trivalent metal oxides can include, but are not limited to,corresponding salts, alkoxides, oxides, and/or hydroxides of thetrivalent metal, e.g., aluminum sulphate, aluminum nitrate, colloidalalumina, aluminum trihydroxide, hydroxylated alumina, Al₂O₃, aluminumhalides (e.g., AlCl₃), NaAlO₂, boron nitride, B₂O₃ and/or H₃BO₃.

In various aspects, the source of trivalent metal oxide may be acompound of formula M³(OX¹⁴)₃ (Va) to obtain an organosilica materialwhich is a copolymer comprising at at least one independent unit Formula(I) as described herein, optionally at least one unit of Formula (II) asdescribed herein, optionally at least one independent unit of Formula(III) as described herein, optionally at least one independent unit ofFormula (IV) as described herein and at least one independent unit ofFormula (V), wherein M³ can be a Group 13 metal and each X¹⁴independently can be a C₁-C₆ alkyl group.

In one embodiment, M³ can be B, Al, Ga, In, Tl, or Uut. In particular,M³ can be Al or B.

Additionally or alternatively, each X¹⁴ can be a C₁-C₆ alkyl group, aC₁-C₅ alkyl group, a C₁-C₄ alkyl group, a C₁-C₃ alkyl group, a C₁-C₂alkyl group or methyl. In particular, each X¹⁴ can be methyl, ethyl,propyl or butyl.

Additionally or alternatively, M³ can be Al or B and each X¹⁴ can bemethyl, ethyl, propyl or butyl.

In a particular embodiment, M³ can be Al and each X¹⁴ can be methyl,such that compound corresponding to Formula (IIa) can be aluminumtrimethoxide.

In a particular embodiment, M³ can be Al and each X¹⁴ can be ethyl, suchthat compound corresponding to Formula (IIa) can be aluminumtriethoxide.

In a particular embodiment, M³ can be Al and each X¹⁴ can be propyl,such that compound corresponding to Formula (IIa) can be aluminumisopropoxide.

In a particular embodiment, M³ can be Al and each X¹⁴ can be butyl, suchthat compound corresponding to Formula (IIa) can be aluminumtri-sec-butoxide.

In another particular embodiment, Formula (Ia) can betris(3-trimethoxy-silylpropyl)isocyanurate and Formula (Va) can beselected from the group consisting of aluminum trimethoxide, aluminumtriethoxide, aluminum isopropoxide, and aluminum tri-sec-butoxide.

In another particular embodiment, Formula (Ia) can betris(3-trimethoxy-silylpropyl)isocyanurate and Formula (Va) can bealuminum tri-sec-butoxide.

Additionally or alternatively, the source of trivalent metal oxide maybe a compound of Formula (X¹⁵O)₂M⁴—O—Si(OX¹⁶)₃ (VIa), to obtain anorganosilica material which is a copolymer comprising at at least oneindependent unit Formula (I) as described herein, optionally at leastone independent unit of Formula (II) as described herein, optionally atleast one independent unit of Formula (III) as described herein,optionally at least one independent unit of Formula (IV) as describedherein, optionally at least one independent unit of Formula (V) and atleast one independent unit of Formula (VI), wherein M⁴ can be a Group 13metal and each X¹⁵ and each X¹⁶ independently can be a C₁-C₆ alkylgroup.

In one embodiment, M⁴ can be B, Al, Ga, In, Tl, or Uut. In particular,M⁴ can be Al or B.

Additionally or alternatively, each X¹⁵ and each X¹⁶ independently canbe a C₁-C₆ alkyl group, a C₁-C₅ alkyl group, a C₁-C₄ alkyl group, aC₁-C₃ alkyl group, a C₁-C₂ alkyl group or methyl. In particular, eachX¹⁵ and each X¹⁶ independently can be methyl, ethyl, propyl or butyl.

Additionally or alternatively, M⁴ can be Al or B and each X¹⁵ and eachX¹⁶ independently can be methyl, ethyl, propyl or butyl.

Additionally or alternatively, the source of a trivalent metal oxide maybe a source of a compound of Formula (IV) (e.g., AlCl₃), and/or a sourceof a compound of Formula (V).

The molar ratio of compound of Formula (Ia) to trivalent metal oxide mayvary within wide limits, such as from about 99:1 to about 1:99, fromabout 30:1 to about 1:1, from about 25:1 to about 1:1, from about 20:1to about 3:1 or from about 20:1 to about 5:1.

III.G. Metal Chelate Sources

In additional embodiments, the methods provided herein can furthercomprise adding to the aqueous solution a source of metal chelatecompounds.

Examples of metal chelate compounds, when present, can include titaniumchelate compounds such as triethoxy.mono(acetylacetonato)titanium,tri-n-propoxy.mono(acetylacetonato)titanium, tri-i-propoxy.mono(acetylacetonato)titanium,tri-n-butoxy.mono(acetylacetonato)titanium,tri-sec-butoxy.mono(acetylacetonato)titanium,tri-t-butoxy.mono(acetylacetonato)titanium,diethoxy.bis(acetylacetonato)titanium,di-n-propoxy.bis(acetylacetonato)titanium,di-i-propoxy.bis(acetylacetonato)titanium,di-n-butoxy.bis(acetylacetonato)titanium,di-sec-butoxy.bis(acetylacetonato)titanium,di-t-butoxy.bis(acetylacetonato)titanium,monoethoxy.tris(acetylacetonato)titanium,mono-n-propoxy.tris(acetylacetonato)titanium,mono-i-propoxy.tris(acetylacetonato)titatium,mono-n-butoxy.tris(acetylacetonato)titanium,mono-sec-butoxy.tris(acetylacetonato)titanium,mono-t-butoxy-tris(acetylacetonato)titanium,tetrakis(acetylacetonato)titanium,triethoxy.mono(ethylacetoacetaato)titanium,tri-n-propoxy.mono(ethylacetoacetato)titanium,tri-i-propoxy.mono(ethylacetoacetato)titanium,tri-n-butoxy.mono(ethylacetoacetato)titanium,tri-sec-butoxy.mono(ethylacetoacetato)titanium,tri-t-butoxy-mono(ethylacetoacetato)titanium,diethoxy.bis(ethylacetoacetato)titanium,di-n-propoxy.bis(ethylacetoacetato)titanium,di-i-propoxy.bis(ethylacetoacetato)titanium,di-n-butoxy.bis(ethylacetoacetato)titanium,di-sec-butoxy.bis(ethylacetoacetato)titanium,di-t-butoxy.bis(ethylacetoacetato)titanium,monoethoxy.tris(ethylacetoacetato)titanium,mono-n-propoxy.tris(ethylacetoaetato)titanium,mono-i-propoxy.tris(ethylacetoacetato)titanium,mono-n-butoxy.tris(ethylacetoacetato)titanium,mono-sec-butoxy.tris(ethylacetoacetato)titanium,mono-t-butoxy.tris(ethylacetoacetato)titanium,tetrakis(ethylacetoacetato)titanium,mono(acetylacetonato)tris(ethylacetoacetato)titanium,bis(acetylacetonato)bis(ethylacetoacetato)titanium, andtris(acetylacetonato)mono(ethylacetoacetato)titanium; zirconium chelatecompounds such as triethoxy.mono(acetylacetonato)zirconium,tri-n-propoxy.mono(acetylacetonato)zirconium,tri-i-propoxy.mono(acetylacetonato)zirconium,tri-n-butoxy.mono(acetylacetonato)zirconium,tri-sec-butoxy.mono(acetylacetonato)zirconium,tri-t-butoxy.mono(acetylacetonato)zirconium,diethoxy.bis(acetylacetonato)zirconium,di-n-propoxy.bis(acetylacetonato)zirconium,di-i-propoxy.bis(acetylacetonato)zirconium,di-n-butoxy.bis(acetylacetonato)zirconium,di-sec-butoxy.bis(acetylacetonato)zirconium,di-t-butoxy.bis(acetylacetonato)zirconium,monoethoxy.tris(acetylacetonato)zirconium,mono-n-propoxy.tris(acetylacetonato)zirconium,mono-i-propoxy.tris(acetylacetonato)zirconium,mono-n-butoxy.tris(acetylacetonato)zirconium,mono-sec-butoxy.tris(acetylacetonato)zirconium,mono-t-butoxy.tris(acetylacetonato)zirconium,tetrakis(acetylacetonato)zirconium,triethoxy.mono(ethylacetoacetato)zirconium,tri-n-propoxy.mono(ethylacetoacetato)zirconium,tri-i-propoxy.mono(ethylacetoacetato)zirconium,tri-n-butoxy.mono(ethylacetoacetato)zirconium,tri-sec-butoxy.mono(ethylacetoacetato)zirconium,tri-t-butoxy.mono(ethylacetoacetato)zirconium,diethoxy.bis(ethylacetoacetato)zirconium,di-n-propoxy.bis(ethylacetoacetato)zirconium,di-i-propoxy.bis(ethylacetoacetato)zirconium,di-n-butoxy.bis(ethylacetoacetato) zirconium,di-sec-butoxy.bis(ethylacetoacetato)zirconium,di-t-butoxy.bis(ethylacetoacetato)zirconium,monoethoxy.tris(ethylacetoacetato)zirconium,mono-n-propoxy.tris(ethylacetoacetato)zirconium,mono-i-propoxy.tris(ethylacetoacetato) zirconium,mono-n-butoxy.tris(ethylacetoacetato)zirconium,mono-sec-butoxy.tris(ethylacetoacetato)zirconium,mono-t-butoxy.tris(ethylacetoacetato)zirconium,tetrakis(ethylacetoacetato)zirconium,mono(acetylacetonato)tris(ethylacetoacetato) zirconium,bis(acetylacetonato)bis(ethylacetoacetato)zirconium, andtris(acetylacetonato)mono(ethylacetoacetato)zirconium; and aluminumchelate compounds such as tris(acetylacetonato)aluminum andtris(ethylacetoacetato)aluminum. Of these, the chelate compounds oftitanium or aluminum can be of note, of which the chelate compounds oftitanium can be particularly of note. These metal chelate compounds maybe used either singly or in combination

III.H. Molar Ratio

In the methods described herein, a molar ratio of Formula (Ia): Formula(IIa), Formula (Ia): Formula (IIIa) of about 99:1 to about 1:99, about75:1 to about 1:99, about 50:1 to about 1:99, about 25:1 to about 1:99,about 15: 1 to about 1:99, about 50:1 to about 1:50, about 25:1 to about1:25 or about 15:1 to about 1:15 may be used. For example, molar ratiosof about 3:2, about 4:1, about 4:3, about 5:1, about 2:3, about 1:1about 5:2 and about 15:1 may be used. For example, a molar ratio ofFormula(Ia): Formula (IIa), and/or Formula (Ia): Formula (IIIa) can beabout 3:2.

For the sake of the following discussion, the compounds of Formula(IIa), (IIIa), (IVa) shall be referred to collectively as startingsiloxane. Depending on the choice of starting materials, the solutionmay have a variety of compositions. For example, if base is used, thesolution may have molar ratios of starting siloxane to OH⁻ of from about1:5 to about 1:20, such as from about 1:5 to about 1:15 or from about1:5 to 1:10, or from about 1:6 to 1:20. If acid is used, the solutionmay have molar ratios of starting siloxane : H⁺of from about 50:1 toabout 5:1, such as from about 45:1 to about 10:1. In both cases whenacid or base is used, the molar ratios of starting siloxane to H₂O mayvary from about 1:50 to about 1:1000, such as from about 1:100 to about1:500.

III.I Aging the Solution

The solution formed in the methods described herein can be aged for atleast about 4 hours, at least about 6 hours, at least about 12 hours, atleast about 18 hours, at least about 24 hours (1 day), at least about 30hours, at least about 36 hours, at least about 42 hours, at least about48 hours (2 days), at least about 54 hours, at least about 60 hours, atleast about 66 hours, at least about 72 hours (3 days), at least about96 hours (4 days), at least about 120 hours (5 days) or at least about144 hours (6 days).

Additionally or alternatively, the solution formed in the methodsdescribed herein can be aged for about 4 hours to about 144 hours (6days), about 4 hours to about 120 hours (5 days), about 4 hours to about96 hours (4 days), about 4 hours to about 72 hours (3 days), about 4hours to about 66 hours , about 4 hours to about 60 hours, about 4 hoursto about 54 hours, about 4 hours to about 48 hours (2 days), about 4hours to about 42 hours, about 4 hours to about 36 hours, about 4 hoursto about 30 hours, about 4 hours to about 24 hours (1 day), about 4hours to about 18 hours, about 4 hours to about 12 hours, about 4 hoursto about 6 hours, about 6 hours to about 144 hours (6 days), about 6hours to about 120 hours (5 days), about 6 hours to about 96 hours (4days), about 6 hours to about 72 hours (3 days), about 6 hours to about66 hours , about 6 hours to about 60 hours, about 6 hours to about 54hours, about 6 hours to about 48 hours (2 days), about 6 hours to about42 hours, about 6 hours to about 36 hours, about 6 hours to about 30hours, about 6 hours to about 24 hours (1 day), about 6 hours to about18 hours, about 6 hours to about 12 hours, about 12 hours to about 144hours (6 days), about 12 hours to about 120 hours (5 days), about 12hours to about 96 hours (4 days), about 12 hours to about 72 hours (3days), about 12 hours to about 66 hours , about 12 hours to about 60hours, about 12 hours to about 54 hours, about 12 hours to about 48hours (2 days), about 12 hours to about 42 hours, about 12 hours toabout 36 hours, about 12 hours to about 30 hours, about 12 hours toabout 24 hours (1 day), about 12 hours to about 18 hours, about 18 hoursto about 144 hours (6 days), about 18 hours to about 120 hours (5 days),about 18 hours to about 96 hours (4 days), about 18 hours to about 72hours (3 days), about 18 hours to about 66 hours , about 18 hours toabout 60 hours, about 18 hours to about 54 hours, about 18 hours toabout 48 hours (2 days), about 18 hours to about 42 hours, about 18hours to about 36 hours, about 18 hours to about 30 hours, about 18hours to about 24 hours (1 day), about 24 hours(1 day) to about 144hours (6 days), about 24 (1 day) hours (1 day) to about 120 hours (5days), about 24 hours (1 day) to about 96 hours (4 days), about 24 hours(1 day) to about 72 hours (3 days), about 24 hours (1 day) to about 66hours , about 24 hours (1 day) to about 60 hours, about 24 hours (1 day)to about 54 hours, about 24 hours (1 day) to about 48 hours (2 days),about 24 hours (1 day) to about 42 hours, about 24 hours (1 day) toabout 36 hours, about 24 hours (1 day) to about 30 hours, about 30 hoursto about 144 hours (6 days), about 30 hours to about 120 hours (5 days),about 30 hours to about 96 hours (4 days), about 30 hours to about 72hours (3 days), about 30 hours to about 66 hours , about 30 hours toabout 60 hours, about 30 hours to about 54 hours, about 30 hours toabout 48 hours (2 days), about 30 hours to about 42 hours, about 30hours to about 36 hours, about 36 hours to about 144 hours (6 days),about 36 hours to about 120 hours (5 days), about 36 hours to about 96hours (4 days), about 36 hours to about 72 hours (3 days), about 36hours to about 66 hours , about 36 hours to about 60 hours, about 36hours to about 54 hours, about 36 hours to about 48 hours (2 days),about 36 hours to about 42 hours, about 42 hours to about 144 hours (6days), about 42 hours to about 120 hours (5 days), about 42 hours toabout 96 hours (4 days), about 42 hours to about 72 hours (3 days),about 42 hours to about 66 hours, about 42 hours to about 60 hours,about 42 hours to about 54 hours, about 42 hours to about 48 hours (2days), about 48 hours (2 days) to about 144 hours (6 days), about 48hours (2 days) to about 120 hours (5 days), about 48 hours (2 days) toabout 96 hours (4 days), about 48 hours (2 days) to about 72 hours (3days), about 48 hours (2 days) to about 66 hours , about 48 hours (2days) to about 60 hours, about 48 hours (2 days) to about 54 hours,about 54 hours to about 144 hours (6 days), about 54 hours to about 120hours (5 days), about 54 hours to about 96 hours (4 days), about 54hours to about 72 hours (3 days), about 54 hours to about 66 hours ,about 54 hours to about 60 hours, about 60 hours to about 144 hours (6days), about 60 hours to about 120 hours (5 days), about 60 hours toabout 96 hours (4 days), about 60 hours to about 72 hours (3 days),about 60 hours to about 66 hours , about 66 hours to about 144 hours (6days), about 66 hours to about 120 hours (5 days), about 66 hours toabout 96 hours (4 days), about 66 hours to about 72 hours (3 days),about 72 hours (3 days) to about 144 hours (6 days), about 72 hours (3days) to about 120 hours (5 days), about 72 hours (3 days) to about 96hours (4 days), about 96 hours (4 days) to about 144 hours (6 days),about 96 hours (4 days) to about 120 hours (5 days), or about 120 hours(5 days) to about 144 hours (6 days).

Additionally or alternatively, the solution formed in the method can beaged at temperature of at least about 10° C., at least about 20° C., atleast about 30° C., at least about 40° C., at least about 50° C., atleast about 60° C., at least about 70° C., at least about 80° C., atleast about 90° C., at least about 100° C., at least about 110° C., atleast about 120° C. at least about 130° C., at least about 140° C., atleast about 150° C., at least about 175° C., at least about 200° C., atleast about 250° C., or about 300° C.

Additionally or alternatively, the solution formed in the method can beaged at temperature of about 10° C. to about 300° C., about 10° C. toabout 250° C., about 10° C. to about 200° C., about 10° C. to about 175°C., about 10° C. to about 150° C., about 10° C. to about 140° C., about10° C. to about 130° C., about 10° C. to about 120° C., about 10° C. toabout 110° C., about 10° C. to about 100° C., about 10° C. to about 90°C., about 10° C. to about 80° C., about 10° C. to about 70° C., about10° C. to about 60° C., about 10° C. to about 50° C., about 20° C. toabout 300° C., about 20° C. to about 250° C., about 20° C. to about 200°C., about 20° C. to about 175° C., about 20° C. to about 150° C., about20° C. to about 140° C., about 20° C. to about 130° C., about 20° C. toabout 120° C., about 20° C. to about 110° C., about 20° C. to about 100°C., about 20° C. to about 90° C., about 20° C. to about 80° C., about20° C. to about 70° C., about 20° C. to about 60° C., about 20° C. toabout 50° C., about 30° C. to about 300° C., about 30° C. to about 250°C., about 30° C. to about 200° C., about 30° C. to about 175° C., about30° C. to about 150° C., about 30° C. to about 140° C., about 30° C. toabout 130° C., about 30° C. to about 120° C., about 30° C. to about 110°C., about 30° C. to about 100° C., about 30° C. to about 90° C., about30° C. to about 80° C., about 30° C. to about 70° C., about 30° C. toabout 60° C., about 30° C. to about 50° C., about 50° C. to about 300°C., about 50° C. to about 250° C., about 50° C. to about 200° C., about50° C. to about 175° C., about 50° C. to about 150° C., about 50° C. toabout 140° C., about 50° C. to about 130° C., about 50° C. to about 120°C., about 50° C. to about 110° C., about 50° C. to about 100° C., about50° C. to about 90° C., about 50° C. to about 80° C., about 50° C. toabout 70° C., about 50° C. to about 60° C., about 70° C. to about 300°C., about 70° C. to about 250° C., about 70° C. to about 200° C., about70° C. to about 175° C., about 70° C. to about 150° C., about 70° C. toabout 140° C., about 70° C. to about 130° C., about 70° C. to about 120°C., about 70° C. to about 110° C., about 70° C. to about 100° C., about70° C. to about 90° C., about 70° C. to about 80° C., about 80° C. toabout 300° C., about 80° C. to about 250° C., about 80° C. to about 200°C., about 80° C. to about 175° C., about 80° C. to about 150° C., about80° C. to about 140° C., about 80° C. to about 130° C., about 80° C. toabout 120° C., about 80° C. to about 110° C., about 80° C. to about 100°C., about 80° C. to about 90° C., about 90° C. to about 300° C., about90° C. to about 250° C., about 90° C. to about 200° C., about 90° C. toabout 175° C., about 90° C. to about 150° C., about 90° C. to about 140°C., about 90° C. to about 130° C., about 90° C. to about 120° C., about90° C. to about 110° C., about 90° C. to about 100° C., about 100° C. toabout 300° C., about 100° C. to about 250° C., about 100° C. to about200° C., about 100° C. to about 175° C., about 100° C. to about 150° C.,about 100° C. to about 140° C., about 100° C. to about 130° C., about100° C. to about 120° C., about 100° C. to about 110° C., about 110° C.to about 300° C., about 110° C. to about 250° C., about 110° C. to about200° C., about 110° C. to about 175° C., about 110° C. to about 150° C.,about 110° C. to about 140° C., about 110° C. to about 130° C., about110° C. to about 120° C., about 120° C. to about 300° C., about 120° C.to about 250° C., about 120° C. to about 200° C., about 120° C. to about175° C., about 120° C. to about 150° C., about 120° C. to about 140° C.,about 120° C. to about 130° C., about 130° C. to about 300° C., about130° C. to about 250° C., about 130° C. to about 200° C., about 130° C.to about 175° C., about 130° C. to about 150° C., or about 130° C. toabout 140° C.

III.J. Drying the Pre-Product

The methods described herein comprise drying the pre-product (e.g., agel) to produce an organosilica material.

In some embodiments, the pre-product (e.g., a gel) formed in the methodcan be dried at a temperature of greater than or equal to about 50° C.,greater than or equal to about 70° C., greater than or equal to about80° C., greater than or equal to about 100° C., greater than or equal toabout 110° C., greater than or equal to about 120° C., greater than orequal to about 150° C., greater than or equal to about 200° C., greaterthan or equal to about 250° C., greater than or equal to about 300° C.,greater than or equal to about 350° C., greater than or equal to about400° C., greater than or equal to about 450° C., greater than or equalto about 500° C., greater than or equal to about 550° C., or greaterthan or equal to about 600° C.

Additionally or alternatively, the pre-product (e.g., a gel) formed inthe method can be dried at temperature of about 50° C. to about 600° C.,about 50° C. to about 550° C., about 50° C. to about 500° C., about 50°C. to about 450° C., about 50° C. to about 400° C., about 50° C. toabout 350° C., about 50° C. to about 300° C., about 50° C. to about 250°C., about 50° C. to about 200° C., about 50° C. to about 150° C., about50° C. to about 120° C., about 50° C. to about 110° C., about 50° C. toabout 100° C., about 50° C. to about 80° C., about 50° C. to about 70°C., about 70° C. to about 600° C., about 70° C. to about 550° C., about70° C. to about 500° C., about 70° C. to about 450° C., about 70° C. toabout 400° C., about 70° C. to about 350° C., about 70° C. to about 300°C., about 70° C. to about 250° C., about 70° C. to about 200° C., about70° C. to about 150° C., about 70° C. to about 120° C., about 70° C. toabout 110° C., about 70° C. to about 100° C., about 70° C. to about 80°C., about 80° C. to about 600° C., about 70° C. to about 550° C., about80° C. to about 500° C., about 80° C. to about 450° C., about 80° C. toabout 400° C., about 80° C. to about 350° C., about 80° C. to about 300°C., about 80° C. to about 250° C., about 80° C. to about 200° C., about80° C. to about 150° C., about 80° C. to about 120° C., about 80° C. toabout 110° C., or about 80° C. to about 100° C.

In a particular embodiment, the pre-product (e.g., a gel) formed in themethod can be dried at temperature from about 70° C. to about 200° C.

Additionally or alternatively, the pre-product (e.g., a gel) formed inthe method can be dried in a N₂ and/or air atmosphere.

III.K. Optional Further Steps

In some embodiments, the method can further comprise calcining theorganosilica material to obtain a silica material. The calcining can beperformed in air or an inert gas, such as nitrogen or air enriched innitrogen. Calcining can take place at a temperatue of at least about300° C., at least about 350° C., at least about 400° C., at least about450° C., at least about 500° C., at least about 550° C., at least about600° C., or at least about 650° C., for example at least about 400° C.Additionally or alternatively, calcining can be performed at atemperature of about 300° C. to about 650° C., about 300° C. to about600° C., about 300° C. to about 550° C., about 300° C. to about 400° C.,about 300° C. to about 450° C., about 300° C. to about 400° C., about300° C. to about 350° C., about 350° C. to about 650° C., about 350° C.to about 600° C., about 350° C. to about 550° C., about 350° C. to about400° C., about 350° C. to about 450° C., about 350° C. to about 400° C.,about 400° C. to about 650° C., about 400° C. to about 600° C., about400° C. to about 550° C., about 400° C. to about 500° C., about 400° C.to about 450° C., about 450° C. to about 650° C., about 450° C. to about600° C., about 450° C. to about 550° C., about 450° C. to about 500° C.,about 500° C. to about 650° C., about 500° C. to about 600° C., about500° C. to about 550° C., about 550° C. to about 650° C., about 550° C.to about 600° C. or about 600° C. to about 650° C.

IV. Organosilica Material Product-By-Process

Organosilica materials can be made from the methods described herein. Inanother particular embodiment, organosilica materials made from anaqueous mixture as described herein that contains essentially nostructure directing agent or porogen as described herein, wherein theorganosilica material may be:

(i) a polymer comprising at least one independent unit of Formula (I) asdescribed herein: or (ii) a copolymer comprising at least oneindependent unit of Formula (I) as described herein and one or more ofthe following monomers:

-   -   (a) at least one independent unit of Formula (II) as described        herein;    -   (b) at least one independent unit of Formula (III) as described        herein;    -   (c) at least one independent unit of Formula (IV) as described        herein;    -   (d) at least one independent unit of Formula (V) as described        herein; or    -   (e) at least one independent unit of Formula (VI) as described        herein.

The organosilica materials made from the methods described herein mayexhibit an XRD pattern as described herein, particularly with only onepeak between about 1 and about 3 degrees 2θ. Additionally oralternatively, the organosilica materials made from the methodsdescribed herein can exhibit substantially no peaks in the range ofabout 0.5 to about 10 degrees 2θ, about 0.5 to about 12 degrees 2θrange, about 0.5 to about 15 degrees 2θ, about 0.5 to about 20 degrees2θ, about 0.5 to about 30 degrees 2θ, about 0.5 to about 40 degrees 2θ,about 0.5 to about 50 degrees 2θ, about 0.5 to about 60 degrees 2θ,about 0.5 to about 70 degrees 2θ, about 2 to about 10 degrees 2θ, about2 to about 12 degrees 2θ range, about 2 to about 15 degrees 2θ, about 2to about 20 degrees 2θ, about 2 to about 30 degrees 2θ, about 2 to about40 degrees 2θ, about 2 to about 50 degrees 2θ, about 2 to about 60degrees 2θ, about 2 to about 70 degrees 2θ, about 3 to about 10 degrees2θ, about 3 to about 12 degrees 2θ range, about 3 to about 15 degrees2θ, about 3 to about 20 degrees 2θ, about 3 to about 30 degrees 2θ,about 3 to about 40 degrees 2θ, about 3 to about 50 degrees 2θ, about 3to about 60 degrees 2θ, or about 3 to about 70 degrees 2θ.

Additionally or alternatively, the organosilica materials may have anaverage pore diameter as described herein, particularly, between about1.5 nm and about 20 nm.

V. Uses of the Organosilica Materials

The organosilica materials described herein find uses in several areas.

In certain embodiments, the organosilica material described herein canbe used as adsorbents or support matrices for separation and/orcatalysis processes.

Additionally or alternatively, the organosilica materials describedherein can be used as a binder for zeolitic and non-zeolitic materialsfor use in separation processes (e.g., sorption) and/or for use incatalysis.

V.A. Color Removal

In some cases, the organosilica materials can be used in a method forreducing impurities in a liquid hydrocarbon product. The method cancomprise contacting a liquid hydrocarbon product with the organosilicamaterial described herein and as prepared according to the methodsdescribed herein. In particular, the organosilica material may compriseunits of Formula (I) and optionally units of Formula (II) and/or Formula(III).

In various aspects, the impurities can be polar compounds and/oraromatic compounds. The polar compounds and/or aromatic compounds maycause discoloration of the liquid hydrocarbon. As used herein, “polarcompound” refers to a compound that has portions of negative and/orpositive charges forming negative and/or positive poles. While a polarcompound does not carry a net electric charge, the electrons areunequally shared between the nuclei. Water is considered a polarcompound in the present invention. Examples of polar compounds, includebut are not limited to nitrogen-containing compounds (e.g., N₂, NH₃,NO₂, pyrrole, pyridine, quinoline, indazole, etc.) and sulfur-containingcompounds (e.g., SO₂, H₂S, thiophene, benzothiophene, dibenzothiophene,etc.). Additionally or alternatively, the aromatic compound can be asingle ring aromatic, a double ring aromatic and/or a multi-ringaromatic (e.g., 3 or more rings). Examples of single ring aromaticcompounds include, but are not limited to, benzene, toulene, furan,pyrrole, thiophene, pyridine, pyrazine, pyrimidine, and triazine.Examples of double ring aromatic compounds include, but are not limitedto, benzothiophene, purine, benzimidazole, indazole, naphthalene,quinoline, and quinoxaline. Examples of multi-ring aromatic compoundsinclude, but are not limited to, anthracene, acridine, phenanthrene,tetracene, chrysene, triphenylene, pyrene, pentacene, coronene, andcorannulene. In particular, multi-ring aromatics are removed from theliquid hydrocarbon. Additionally or alternatively, the organosilicamaterial can have a selectivity for multi-ring aromatics compared tosingle ring aromatics of at least about 1.1, at least about 1.2. atleast about 1.4, at least about 1.5, at least about 1.6, at least about1.8, at least about 2.0, at least about 2.5, at least about 3.0, or atleast about 4.0. Additionally or alternatively, the organosilicamaterial can have a selectivity for multi-ring aromatics compared tosingle ring aromatics of at least about 1.1 to about 4.0, at least about1.1 to about 3.0, at least about 1.2 to about 2.5, at least about 1.1 toat least about 2.0, or at least about 1.1 to at least about 1.8.

Additionally or alternatively, the liquid hydrocarbon may comprisediesel fuel, jet fuel and/or gasoline. In particular, the liquidhydrocarbon may comprise diesel fuel. With regard to diesel fuel, coloris one of the specifications for the final products. Color level of theliquid hydrocarbon product (e.g., diesel fuel) may be measured accordingto D6045 ASTM.

Thus, in various aspects, the liquid hydrocarbon product (e.g., dieselfuel) following contact with the organosilica material as describedherein may have a color level as measured according to D6045 ASTM ofless than or equal to about 4.0, less than or equal to about 3.5, lessthan or equal to about 3.0, less than or equal to about 2.5, less thanor equal to about 2.0, less than or equal to about 1.5, less than orequal to about 1.0, or less than equal to about 0.1 or about 0.0. Inparticular, the liquid hydrocarbon product (e.g., diesel fuel) followingcontact with the organosilica material as described herein may have acolor level as measured according to D6045 ASTM of less than or equal toabout 3.0 or less than or equal to about 2.5.

Additionally or alternatively, the liquid hydrocarbon product (e.g.,diesel fuel) following contact with the organosilica material asdescribed herein may have a color level as measured according to D6045ASTM of about 0.0 to about 4.0, about 0.0 to about 3.0, about 0.0 toabout 2.0, about 0.0 to about 1.0, about 0.1 to about 4.0, about 0.1 toabout 3.0, about 0.1 to about 2.0, about 0.0 to about 1.0, about 0.5 toabout 4.0, about 0.5 to about 3.5, about 0.5 to about 3.0, about 0.5 toabout 2.5, about 0.5 to about 2.0, about 0.5 to about 1.5, about 0.5 toabout 1.0, about 1.0 to about 4.0, about 1.0 to about 3.5, about 1.0 toabout 3.0, about 1.0 to about 2.5, about 1.0 to about 2.0, about 1.0 toabout 1.5, about 1.5 to about 4.0, about 1.5 to about 3.5, about 1.5 toabout 3.0, about 1.5 to about 2.5, about 1.5 to about 2.0, about 2.0 toabout 4.0, about 2.0 to about 3.5, about 2.0 to about 3.0, or about 2.0to about 2.5.

In some cases, discoloration in the liquid hydrocarbon product (e.g.,diesel fuel) may be due to aromatic compounds (e.g., multi-ringaromatic) and/or polar compounds present in the liquid hydrocarbonproduct at various sulfur levels. Thus, the liquid hydrocarbon product(e.g., diesel fuel) prior to contact with the organosilica materialdescribed herein may comprise less than or equal to about 50 ppm sulfur,less than or equal to about 45 ppm sulfur, less than or equal to about40 ppm sulfur, less than or equal to about 35 ppm sulfur, less than orequal to about 30 ppm sulfur, less than or equal to about 25 ppm sulfur,less than or equal to about 20 ppm sulfur, less than or equal to about 8ppm sulfur, less than or equal to about 15 ppm sulfur, less than orequal to about 10 ppm sulfur, less than or equal to about 8 ppm sulfur,less than or equal to about 5 ppm sulfur, less than or equal to about 3ppm sulfur, less than or equal to about 2 ppm sulfur, less than or equalto about 1 ppm sulfur, or less than or equal to about 0.1 ppm sulfur.Particularly, the liquid hydrocarbon product (e.g., diesel fuel) priorto contact with the organosilica material described herein may compriseless than or equal to about 20 ppm sulfur or less than or equal to about10 ppm sulfur.

Additionally or alternatively, the liquid hydrocarbon product (e.g.,diesel fuel) prior to contact with the organosilica material describedherein may comprise about 0.1 ppm to about 50 ppm sulfur, about 0.1 ppmto about 40 ppm sulfur, about 0.1 ppm to about 30 ppm sulfur, about 0.1ppm to about 25 ppm sulfur, about 0.1 ppm to about 20 ppm sulfur, about0.1 ppm to about 18 ppm sulfur, about 0.1 ppm to about 16 ppm sulfur,about 0.1 ppm to about 14 ppm sulfur, about 0.1 ppm to about 12 ppmsulfur, about 0.1 ppm to about 10 ppm sulfur, about 0.1 ppm to about 9ppm sulfur, about 0.1 ppm to about 8 ppm sulfur, about 0.1 ppm to about7 ppm sulfur, about 0.1 ppm to about 6 ppm sulfur, about 0.1 ppm toabout 5 ppm sulfur, about 0.1 ppm to about 4 ppm sulfur, about 0.1 ppmto about 3 ppm sulfur, about 0.1 ppm to about 2 ppm sulfur, about 0.1ppm to about 1 ppm sulfur, about 1 ppm to about 40 ppm sulfur, about 1ppm to about 40 ppm sulfur, about 1 ppm to about 30 ppm sulfur, about 1ppm to about 25 ppm sulfur, about 1 ppm to about 20 ppm sulfur, about 1ppm to about 18 ppm sulfur, about 1 ppm to about 16 ppm sulfur, about 1ppm to about 14 ppm sulfur, about 1 ppm to about 12 ppm sulfur, about 1ppm to about 10 ppm sulfur, about 1 ppm to about 9 ppm sulfur, about 1ppm to about 8 ppm sulfur, about 1 ppm to about 7 ppm sulfur, about 1ppm to about 6 ppm sulfur, about 1 ppm to about 5 ppm sulfur, about 1ppm to about 4 ppm sulfur, about 1 ppm to about 3 ppm sulfur, about 1ppm to about 2 ppm sulfur, about 2 ppm to about 40 ppm sulfur, about 2ppm to about 40 ppm sulfur, about 2 ppm to about 30 ppm sulfur, about 2ppm to about 25 ppm sulfur, about 2 ppm to about 20 ppm sulfur, about 2ppm to about 18 ppm sulfur, about 2 ppm to about 16 ppm sulfur, about 2ppm to about 14 ppm sulfur, about 2 ppm to about 12 ppm sulfur, about 2ppm to about 10 ppm sulfur, about 2 ppm to about 9 ppm sulfur, about 2ppm to about 8 ppm sulfur, about 2 ppm to about 7 ppm sulfur, about 2ppm to about 6 ppm sulfur, about 2 ppm to about 5 ppm sulfur, about 2ppm to about 4 ppm sulfur, about 2 ppm to about 3 ppm sulfur, about 5ppm to about 40 ppm sulfur, about 5 ppm to about 40 ppm sulfur, about 5ppm to about 30 ppm sulfur, about 5 ppm to about 25 ppm sulfur, about 5ppm to about 20 ppm sulfur, about 5 ppm to about 18 ppm sulfur, about 5ppm to about 16 ppm sulfur, about 5 ppm to about 14 ppm sulfur, about 5ppm to about 12 ppm sulfur, about 5 ppm to about 10 ppm sulfur, about 5ppm to about 9 ppm sulfur, about 5 ppm to about 8 ppm sulfur, about 5ppm to about 7 ppm sulfur, or about 5 ppm to about 6 ppm sulfur,

Additionally or alternatively, single ring aromatics, double ringaromatics or multi-ring aromatics, separately or together, may beremoved from a liquid hydrocarbon product (e.g., diesel fuel) in anamount of less than about 1 wt. %, less than about 2 wt. %, less thanabout 4 wt. %, less than about 5 wt. %, less than about 6 wt. %, lessthan about 8 wt. %, or less than about 10 wt. %, In particular,multi-ring aromatics may be removed from a liquid hydrocarbon product(e.g., diesel fuel) in amount of less than about 1 wt. %,

Additionally or alternatively, single ring aromatics, double ringaromatics or multi-ring aromatics, separately or together, may beremoved from a liquid hydrocarbon product (e.g., diesel fuel) in amountof about 1 wt. % to about 10 wt. %, about 1 wt. % to about 8 wt. %,about 1 wt. % to about 6 wt. %, about 1 wt. % to about 5 wt. %, about 1wt. % to about 4 wt. %, about 1 wt. % to about 3 wt. %, about 1 wt. % toabout 2wt. %, about 2 wt. % to about 10 wt. %, about 2 wt. % to about 8wt. %, about 2 wt. % to about 6 wt. %, about 2 wt. % to about 5 wt. %,about 2 wt. % to about 4 wt. %, about 2 wt. % to about 3 wt. %, about 3wt. % to about 10 wt. %, about 3 wt. % to about 8 wt. %, about 3 wt. %to about 6 wt. %, about 3 wt. % to about 5 wt. %, about 3 wt. % to about4 wt. %, about 4 wt. % to about 10 wt. %, about 4 wt. % to about 8 wt.%, about 4 wt. % to about 6 wt. %, about 4 wt. % to about 5 wt. %, about5 wt. % to about 10 wt. %, about 5 wt. % to about 8 wt. %, about 5 wt. %to about 6 wt. %, about 6 wt. % to about 10 wt. %, about 6 wt. % toabout 8 wt. %, or about 8 wt. % to about 10 wt. %.

In various aspects, a liquid hydrocarbon product (e.g., diesel fuel) maybe contacted with the organosilica material described herein at atemperature of at least about 10° C., at least about 12° C., at leastabout 14° C., at least about 16° C., at least about 18° C., at leastabout 20° C., at least about 22° C., at least about 24° C., at leastabout 26° C., at least about 28° C., at least about 30° C., at leastabout 32° C., at least about 34° C., at least about 36° C., at leastabout 38° C., at least about 40° C., at least about 45° C., at leastabout 50° C., at least about 55° C., at least about 60° C., at leastabout 65° C., at least about 70° C., at least about 75° C., or at leastabout 80° C. In particular, a liquid hydrocarbon product (e.g., dieselfuel) may be contacted with the organosilica material described hereinat a temperature about 10° C. to about 80° C., particularly about 12° C.to about 40° C., particularly about 14° C. to about 36° C., particularlyabout 18° C. to about 28° C. or particularly about 20° C. to about 28°C.

Additionally or alternatively, a liquid hydrocarbon product (e.g.,diesel fuel) may be contacted with the organosilica material describedherein at a temperature described above and at a pressure of at leastabout 2 psi, at least about 4 psi, at least about 5 psi, at least about6 psi, at least about 8 psi, at least about 10 psi, at least about 12psi, at least about 14 psi, at least about 16 psi, at least about 18psi, at least about 20 psi, at least about 25 psi, or at least about 30psi. In particular, a liquid hydrocarbon product (e.g., diesel fuel) maybe contacted with the organosilica material described herein at atemperature described above and at a pressure of about 2 psi to about 30psi, particularly about 4 psi to about 25 psi, particularly about 5 psito about 16 psi or particularly about 6 psi to about 14 psi.

In various aspects, the organosilica material may be packed into acolumn and the liquid hydrocarbon product (e.g., diesel fuel) may becontacted therein. Additionally or alternatively, the liquid hydrocarbonproduct (e.g., diesel fuel) may be contacted with organosilica materialfollowing hydrotreatment of the liquid hydrocarbon product (e.g., dieselfuel).

In another embodiment, a method for improving color in a diesel fuelproduct is provided herein. The method comprises contacting the dieselfuel product with the organosilica material as described hereinresulting in an improved color diesel fuel product. An “improved colordiesel fuel product” refers to a diesel fuel product with a lower colorlevel as measured according to D6045 ASTM following contact with theorganosilica material as described herein. For example, if a diesel fuelproduct initially has a color level of 5 as measured according to D6045ASTM prior to contact with the organosilica material, an improved colordiesel fuel product would have a color level of less than 5 as measuredaccording to D6045 ASTM following contact with the organosilicamaterial. In particular, the organosilica material may comprise units ofFormula (I) and optionally units of Formula (II) and/or Formula (III).

In various aspects, the diesel fuel product may be contacted with theorganosilica material as described herein at a temperature as describedherein (e.g., about 18° C. to about 28° C.) and/or a pressure asdescribed herein (e.g., about 5 psi to about 16 psi). Additionally oralternatively, the diesel fuel product may be contacted with theorganosilica material following hydrotreatment of the diesel fuel. Theorganosilica material may be packed into a column.

The diesel fuel product may have a color level as measured according toD6045 ASTM prior to contact with the organosilica material of at leastabout 3.0, at least about 3.5, at least about 4.0, at least about 4.5,at least about 5.0, at least about 5.5, at least about 6.0, at leastabout 6.5, at least about 7.0, at least about 7.5, at least about 8.0,at least about 9.0, or at least about 10. In particular, the diesel fuelproduct may have a color level as measured according to D6045 ASTM priorto contact with the organosilica material of at least about 5.0.Additionally or alternatively, the diesel fuel product may have a colorlevel as measured according to D6045 ASTM prior to contact with theorganosilica material of about 3.0 to about 10, about 3.5 to about 10,about 4.0 to about 10 or about 5.0 to about 10.

Additionally or alternatively, the improved color diesel fuel productmay have color as measured according to D6045 ASTM following contactwith the oganosilica material as described as described above, e.g., acolor level as measured according to D6045 ASTM of less than or equal toabout 3.0, or less than or equal to about 2.5.

V.B. Gas Separation Processes

In some cases, the organosilica materials can be used in a gasseparation process as provided herein. The gas separation process cancomprise contacting a gas mixture containing at least one contaminantwith the organosilica material described herein as prepared according tothe methods described herein.

In various embodiments, the gas separation process can be achieved byswing adsorption processes, such as pressure swing adsorption (PSA) andtemperature swing adsorption (TSA). All swing adsorption processestypically have an adsorption step in which a feed mixture (typically inthe gas phase) is flowed over an adsorbent to preferentially adsorb amore readily adsorbed component relative to a less readily adsorbedcomponent. A component may be more readily adsorbed because of kineticor equilibrium properties of the adsorbent. The adsorbent can typicallybe contained in a contactor that is part of the swing adsorption unit.The contactor can typically contain an engineered structured adsorbentbed or a particulate adsorbent bed. The bed can contain the adsorbentand other materials such as other adsorbents, mesopore fillingmaterials, and/or inert materials used to mitigated temperatureexcursions from the heat of adsorption and desorption. Other componentsin the swing adsorption unit can include, but are not necessarilylimited to, valves, piping, tanks, and other contactors. Swingadsorption processes are described in detail in U.S. Pat. Nos.8,784,533; 8,784,534; 8,858,683; and 8,784,535, each of which areincorporated herein by reference. Examples of processes that can be usedherein either separately or in combination are PSA, TSA, pressuretemperature swing adsorption (PTSA), partial purge displacement swingadsorption (PPSA), PPTSA, rapid cycle PSA (RCPSA), RCTSA, RCPPSA andRCPTSA.

Swing adsorption processes can be applied to remove a variety of targetgases, also referred to as “contaminant gas” from a wide variety of gasmixtures. Typically, in binary separation systems, the “light component”as utilized herein is taken to be the species or molecular component(s)not preferentially taken up by the adsorbent in the adsorption step ofthe process. Conversely in such binary systems, the “heavy component” asutilized herein is typically taken to be the species or molecularcomponent(s) preferentially taken up by the adsorbent in the adsorptionstep of the process. However, in binary separation systems where thecomponent(s) that is(are) preferentially adsorbed has(have) a lowermolecular weight than the component(s) that is(are) not preferentiallyadsorbed, those descriptions may not necessarily correlate as disclosedabove.

An example of gas mixture that can be separated in the methods describedherein is a gas mixture comprising CH₄, such as a natural gas stream. Agas mixture comprising CH₄ can contain significant levels ofcontaminants such as H₂O, H₂S, CO₂, N₂, mercaptans, and/or heavyhydrocarbons. Additionally or alternatively, the gas mixture cancomprise NO_(x) and/or SO_(x) species as contaminants, such as a wastegas stream, a flue gas stream and a wet gas stream. As used herein, theterms “NO_(x)” and “NO_(x)” species refers to the various oxides ofnitrogen that may be present in waste gas, such as waste gas fromcombustion processes. The terms refer to all of the various oxides ofnitrogen including, but not limited to, nitric oxide (NO), nitrogendioxide (NO₂), nitrogen peroxide (N₂O), nitrogen pentoxide (N₂O₅), andmixtures thereof. As used herein, the terms “SO_(x),” and “SO_(x)species,” refers to the various oxides of sulfur that may be present inwaste gas, such as waste gas from combustion processes. The terms referto all of the various oxides of sulfur including, but not limited to,SO, SO₂, SO₃, SO₄, S₇O₂ and S₆O₂. Thus, examples of contaminantsinclude, but are not limited to H₂O, H₂S, CO₂, N₂, mercaptans, heavyhydrocarbons, NO_(x) and/or SO_(x) species.

V.B. Aromatic Hydrogenation Process

The hydrogenation catalyst can further comprise a binder such as, butnot limited to, active and inactive materials, inorganic materials,clays, ceramics, activated carbon, alumina, silica, silica-alumina,titania, zirconia, niobium oxide, tantalum oxide, or a combinationthereof, particularly, silica-alumina, alumina, titania, or zirconia.These hydrogenation catalysts can be used for both hydrogenation andaromatic saturation of a feedstream.

In various embodiments, the hydrogenation process can be achieved bycontacting a hydrocarbon feedstream comprising aromatics with ahydrogenation catalyst described herein in the presence of ahydrogen-containing treat gas in a first reaction stage operated undereffective aromatics hydrogenation conditions to produce a reactionproduct with reduced aromatics content.

Hydrogen-containing treat gasses suitable for use in a hydrogenationprocess can be comprised of substantially pure hydrogen or can bemixtures of other components typically found in refinery hydrogenstreams. It is preferred that the hydrogen-containing treat gas streamcontains little, more preferably no, hydrogen sulfide. Thehydrogen-containing treat gas purity should be at least about 50% byvolume hydrogen, preferably at least about 75% by volume hydrogen, andmore preferably at least about 90% by volume hydrogen for best results.It is most preferred that the hydrogen-containing stream besubstantially pure hydrogen.

Feedstreams suitable for hydrogenation by the hydrogenation catalystdescribed herein include any conventional hydrocarbon feedstreams wherehydrogenation or aromatic saturation is desirable. Typically, an inputfeed for an aromatic saturation process can be generated as a product orside-product from a previous type of hydroprocessing, such ashydrocracking for fuels or lubricant base stock production. A wide rangeof petroleum and chemical feedstocks can be hydroprocessed. Suchfeedstreams can include hydrocarbon fluids, diesel, kerosene,lubricating oil feedstreams, heavy coker gasoil (HKGO), de-asphalted oil(DAO), FCC main column bottom (MCB), steam cracker tar. Such feedstreamscan also include other distillate feedstreams such as light to heavydistillates including raw virgin distillates, wax-containing feedstreamssuch as feeds derived from crude oils, shale oils and tar sands.Synthetic feeds such as those derived from the Fischer-Tropsch processcan also be aromatically saturated using the hydrogenation catalystdescribed herein. Typical wax-containing feedstocks for the preparationof lubricating base oils have initial boiling points of about 315° C. orhigher, and include feeds such as whole and reduced petroleum crudes,hydrocrackates, raffinates, hydrotreated oils, gas oils (such asatmospheric gas oils, vacuum gas oils, and coker gas oils), atmosphericand vacuum residues, deasphalted oils/residua (e.g., propane deasphaltedresidua, brightstock, cycle oil), dewaxed oils, slack waxes andFischer-Tropsch wax, and mixtures of these materials. Such feeds may bederived from distillation towers (atmospheric and vacuum),hydrocrackers, hydrotreaters and solvent extraction units, and may havewax contents of up to 50% or more. Preferred lubricating oil boilingrange feedstreams include feedstreams which boil in the range of650-1100° F. Diesel boiling range feedstreams include feedstreams whichboil in the range of 480-660° F. Kerosene boiling range feedstreamsinclude feedstreams which boil in the range of 350-617° F.

Hydrocarbon feedstreams suitable for use herein also contain aromaticsand nitrogen- and sulfur-contaminants. Feedstreams containing up to 0.2wt. % of nitrogen, based on the feedstream, up to 3.0 wt. % of sulfur,and up to 50 wt. % aromatics can be used in the present process Invarious embodiments, the sulfur content of the feedstreams can be belowabout 500 wppm, or below about 300 wppm, or below about 200 wppm, orbelow about 100 wppm, or below about 50 wppm, or below about 15 wppm.The pressure used during an aromatic hydrogenation process can bemodified based on the expected sulfur content in a feedstream. Feedshaving a high wax content typically have high viscosity indexes of up to200 or more. Sulfur and nitrogen contents may be measured by standardASTM methods D2622 (sulfur), and D5453 and/or D4629 (nitrogen),respectively.

Effective hydrogenation conditions may be considered to be thoseconditions under which at least a portion of the aromatics present inthe hydrocarbon feedstream are saturated, preferably at least about 50wt. % of the aromatics are saturated, more preferably greater than about75 wt. %. Effective hydrogenation conditions can include temperatures offrom 150° C. to 400° C., a hydrogen partial pressure of from 740 to20786 kPa (100 to 3000 psig), a space velocity of from 0.1 to 10 liquidhourly space velocity (LHSV), and a hydrogen to feed ratio of from 89 to1780 m³/m³ (500 to 10000 scf/B).

Additionally or alternatively, effective hydrogenation conditions may beconditions effective at removing at least a portion of the nitrogen andorganically bound sulfur contaminants and hydrogenating at least aportion of said aromatics, thus producing at least a liquid lube boilingrange product having a lower concentration of aromatics and nitrogen andorganically bound sulfur contaminants than the lube boiling rangefeedstream.

Additionally or alternatively, effective hydrogenation conditions may beconditions effective at removing at least a portion of the nitrogen andorganically bound sulfur contaminants and hydrogenating at least aportion of said aromatics, thus producing at least a liquid dieselboiling range product having a lower concentration of aromatics andnitrogen and organically bound sulfur contaminants than the dieselboiling range feedstream.

As stated above, in some instances, the hydrocarbon feedstream (e.g.,lube oil boiling range) may be hydrotreated to reduce the sulfurcontaminants to below about 500 wppm, particularly below about 300 wppm,particularly below about 200 wppm or particularly below about 100 wppm.In such an embodiment, the process may comprise at least two reactionstages, the first reaction state containing a hydrotreating catalystoperated under effective hydrotreating conditions, and the secondcontaining a hydrogenation catalyst has described herein operated undereffective hydrogenation conditions as described above. Therefore, insuch an embodiment, the hydrocarbon feedstream can be first contactedwith a hydrotreating catalyst in the presence of a hydrogen-containingtreat gas in a first reaction stage operated under effectivehydrotreating conditions in order to reduce the sulfur content of thefeedstream to within the above-described range. Thus, the term“hydrotreating” as used herein refers to processes wherein ahydrogen-containing treat gas is used in the presence of a suitablecatalyst that is active for the removal of heteroatoms, such as sulfur,and nitrogen. Suitable hydrotreating catalysts for use in the presentinvention are any conventional hydrotreating catalyst and includes thosewhich are comprised of at least one Group 8 metal, preferably Fe, Co andNi, more preferably Co and/or Ni, and most preferably Ni; and at leastone Group 6 metal, preferably Mo and W, more preferably Mo, on a highsurface area support material, preferably alumina. Additionally oralternatively, more than one type of hydrotreating catalyst can be usedin the same reaction vessel. The Group 8 metal may typically be presentin an amount ranging from about 2 to 20 wt. %, preferably from about 4to 12 wt. %. The Group 6 metal can typically be present in an amountranging from about 5 to 50 wt. %, preferably from about 10 to 40 wt. %,and more preferably from about 20 to 30 wt. %. All metals weightpercents are “on support” as described above.

Effective hydrotreating conditions may be considered to be thoseconditions that can effectively reduce the sulfur content of thefeedstream (e.g., lube oil boiling range) to within the above-describedranges. Typical effective hydrotreating conditions can includetemperatures ranging from about 150° C. to about 425° C., preferablyabout 200° C. to about 370° C., more preferably about 230° C. to about350° C. Typical weight hourly space velocities (“WHSV”) may range fromabout 0.1 to about 20 hr⁻¹, preferably from about 0.5 to about 5 hr⁻¹.Any effective pressure can be utilized, and pressures can typicallyrange from about 4 to about 70 atmospheres (405 to 7093 kPa), preferably10 to 40 atmospheres (1013 to 4053 kPa). In a particular embodiment,said effective hydrotreating conditions may be conditions effective atremoving at least a portion of said organically bound sulfurcontaminants and hydrogenating at least a portion of said aromatics,thus producing at least a reaction product (e.g., liquid lube oilboiling range product) having a lower concentration of aromatics andorganically bound sulfur contaminants than the lube oil boiling rangefeedstream.

The contacting of the hydrocarbon feedstream with the hydrotreatingcatalyst may produce a reaction product comprising at least a vaporproduct and a liquid product. The vapor product may typically comprisegaseous reaction products, such as H₂S, and the liquid reaction productmay typically comprise a liquid hydrocarbon having a reduced level ofnitrogen and sulfur contaminants. The total reaction product can bepassed directly into the second reaction stage, but it may be preferredthat the gaseous and liquid reaction products be separated, and theliquid reaction product conducted to the second reaction stage. Thus, inone embodiment, the vapor product and the liquid product may beseparated, and the liquid product may be conducted to the secondreaction stage. The method of separating the vapor product from theliquid product can be accomplished by any means known to be effective atseparating gaseous and liquid reaction products. For example, astripping tower or reaction zone can be used to separate the vaporproduct from the liquid product (e.g., liquid lube oil boiling rangeproduct). The liquid product thus conducted to the second reaction stagecan have a sulfur concentration within the range of about 500 wppm,particularly below about 300 wppm, or particularly below about 200 wppmor particularly below about 100 wppm.

In still other embodiments, the hydrogenation catalysts described hereincan be used in integrated hydroprocessing methods. In addition to thehydrofinishing and/or aromatic hydrogenation/saturation processesinvolving the hydrogenation catalyst described herein, an integratedhydroprocessing method can also include various combinations ofhydrotreating, hydrocracking, catalytic dewaxing (such ashydrodewaxing), and/or solvent dewaxing. The scheme of hydrotreatingfollowed by hydrofinishing described above represents one type ofintegrated process flow. Another integrated processing example is tohave a dewaxing step, either catalytic dewaxing or solvent dewaxing,followed by hydroprocessing with the hydrogenation catalysts describedherein. Still another example is a process scheme involvinghydrotreating, dewaxing (catalytic or solvent), and then hydroprocessingwith the hydrogenation catalysts described herein. Yet another exampleis hydroprocessing with the hydrogenation catalysts described hereinfollowed by dewaxing (catalytic or solvent). Alternatively, multiplehydrofinishing and/or aromatic hydrogenation steps can be employed withhydrotreatment, hydrocracking, or dewaxing steps. An example of such aprocess flow is hydrofinishing, dewaxing (catalytic or solvent), andthen hydrofinishing again, where at least one of the hydrofinishingsteps may use a hydrogenation catalysts described herein. For processesinvolving catalytic dewaxing, effective catalytic dewaxing conditionscan include temperatures of from 150° C. to 400° C., preferably 250° C.to 350° C., pressures of from 791 to 20786 kPa (100 to 3000 psig),preferably 1480 to 17338 kPa (200 to 2500 psig), liquid hourly spacevelocities of from 0.1 to 10 hr⁻¹, preferably 0.1 to 5 hr⁻¹ and hydrogentreat gas rates from 45 to 1780 m³/m³ (250 to 10000 scf/B), preferably89 to 890 m³/m³ (500 to 5000 scf/B). Any suitable dewaxing catalyst maybe used.

In embodiments where the product of an aromatic saturation process willbe a lubricant base oil, the input feed should also have suitablelubricant base oil properties. For example, an input feed intended foruse as a Group I or Group II base oil can have a viscosity index (VI) ofat least about 80, preferably at least about 90 or at least about 95. Aninput feed intended for use as a Group I+base oil can have a VI of atleast about 100, while an input feed intended for use as a Group II+baseoil can have a VI of at least 110. The viscosity of the input feed canbe at least 2 cSt at 100° C., or at least 4 cSt at 100° C., or at least6 cSt at 100° C.

VI. Further Embodiments

The invention can additionally or alternately include one or more of thefollowing embodiments.

Embodiment 1. An organosilica material, which is a polymer of at leastone independent cyclic polyurea monomer of Formula

wherein each R¹ independently is a Z¹OZ²Z³SiZ⁴ group, wherein

each Z¹ represents a hydrogen atom, a C₁-C₄ alkyl group, or a bond to asilicon atom of another monomer unit; each Z² and Z³ independentlyrepresent a hydroxyl group, a C₁-C₄ alkyl group, a C₁-C₄ alkoxy group oran oxygen atom bonded to a silicon atom of another monomer unit; andeach Z⁴ represents a C₁-C₈ alkylene group bonded to a nitrogen atom ofthe cyclic polyurea; and optionally at least one other monomer selectedfrom the group consisting of:

(i) an independent unit of Formula [Z⁵OZ⁶SiCH₂]₃ (II), wherein each Z⁵represents a hydrogen atom, a C₁-C₄ alkyl or a bond to a silicon atom ofanother monomer, and each Z⁶ represents a hydroxyl group, a C₁-C₄ alkylgroup, a C ₁-C₄ alkoxy group, or an oxygen atom bonded to a silicon atomof another monomer;

(ii) an independent unit of Formula Z⁷OZ⁸Z⁹Z¹⁰Si (III), wherein each Z⁷represents a hydrogen atom, a C₁-C₄ alkyl group or a bond to a siliconatom of another monomer; and Z⁸, Z⁹ and Z¹⁰ are each independentlyselected from the group consisting of a hydroxyl group, a C₁-C₄ alkylgroup, a C₁-C₄ alkoxy group, a nitrogen-containing C₁-C₁₀ alkyl group, anitrogen-containing heteroaralkyl group, and a nitrogen-containingoptionally substituted heterocycloalkyl group, and an oxygen atom bondedto a silicon atom of another monomer;

(iii) an independent unit of Formula Z¹¹Z¹²Z¹³Si—R²—SiZ¹¹Z¹²Z¹³ (IV),wherein each Z¹¹ independently represents a hydroxyl group, a C₁-C₄alkoxy group or an oxygen bonded to a silicon atom of another comonomer;each Z¹² and Z¹³ independently represent a hydroxyl group, a C₁-C₄alkoxy group, a C₁-C₄ alkyl group or an oxygen bonded to a silicon atomof another monomer; and R² a C₁-C₈ alkylene group, a C₂-C₈ alkenylenegroup, a C₂-C₈ alkynylene group, a nitrogen-containing C₂-C₁₀ alkylenegroup, an optionally substituted C₆-C₂₀ aralkyl and an optionallysubstituted C₄-C₂₀ heterocycloalkyl group;

(iv) an independent unit of Formula M¹(OZ¹⁴)(V), wherein M¹ represents aGroup 13 metal and each Z¹⁴ independently represents a hydrogen atom, aC₁-C₆ alkyl or a bond to a silicon atom of another monomer;

(v) an independent unit of Formula (Z¹⁵O)₂M²-O—Si(OZ¹⁶)₃ (VI), whereinM² represents a Group 13 metal and each Z¹⁵ and each Z¹⁶ independentlyrepresent a hydrogen atom, a C₁-C₆ alkyl group or a bond to a siliconatom of another monomer; and

(vi) a combination thereof.

Embodiment 2. The organosilica material of embodiment 1, wherein each Z¹represents a hydrogen atom, a C₁-C₂ alkyl group or a bond to a siliconatom of another monomer unit; each Z² and Z³ independently represent ahydroxyl group, a C₁-C₂ alkyl group, a C₁-C₂ alkoxy group or an oxygenatom bonded to a silicon atom of another monomer unit and each Z⁴represents a C₁-C₄ alkylene group bonded to a nitrogen atom of thecyclic polyurea.

Embodiment 3. The organosilica material of embodiment 1 or 2, whereineach Z¹ represents a hydrogen atom, methyl or a bond to a silicon atomof another monomer unit; each Z² and Z³ independently represent ahydroxyl group, methoxy or an oxygen atom bonded to a silicon atom ofanother monomer unit and each Z⁴ represents —CH₂CH₂CH₂— bonded to anitrogen atom of the cyclic polyurea.

Embodiment 4. The organosilica material of any one of the previousembodiments, wherein at least one independent unit of Formula (II) ispresent, wherein each Z⁵ represents a hydrogen atom, a C₁-C₂ alkyl or abond to a silicon atom of another comonomer, and each Z⁶ represents ahydroxyl group, a C₁-C₂ alkyl group, a C₁-C₂ alkoxy group or an oxygenbonded to a silicon atom of another monomer.

Embodiment 5. The organosilica material of embodiment 4, wherein each Z⁵represent a hydrogen atom, ethyl or a bond to a silicon atom of anothermonomer and each Z⁶ represents a hydroxyl group, methyl, ethoxy or anoxygen bonded to a silicon atom of another monomer.

Embodiment 6. The organosilica material of embodiment 4, wherein each Z⁵represent a hydrogen atom, ethyl or a bond to a silicon atom of anothermonomer and each Z⁶ represents a hydroxyl group, ethoxy or an oxygenbonded to a silicon atom of another monomer.

Embodiment 7. The organosilica material of embodiment 4, wherein each Z⁵represent a hydrogen atom, ethyl or a bond to a silicon atom of anothermonomer and each Z⁶ represents methyl.

Embodiment 8. The organosilica material of any one of the previousembodiments, wherein at least one independent unit of Formula (III) ispresent, wherein each Z⁷ represents a hydrogen atom, a C₁-C₂ alkyl groupor a bond to a silicon atom of another comonomer; and Z⁸, Z⁹ and Z¹⁰ areeach independently selected from the group consisting of a hydroxylgroup, a C₁-C₂ alkyl group, C₁-C₂ alkoxy group, a nitrogen-containingC₃-C₁₀ alkyl group, a nitrogen-containing C₄-C₁₀ heteroaralkyl group, ora nitrogen-containing optionally substituted C₄-C₁₀ heterocycloalkylgroup, and an oxygen atom bonded to a silicon atom of another monomer.

Embodiment 9. The organosilica material of embodiment 8, wherein each Z⁷represents a hydrogen atom, methyl, ethyl, or a bond to a silicon atomof another comonomer; and Z⁸, Z⁹ and Z¹⁰ are each independently selectedfrom the group consisting of a hydroxyl group, methoxy, ethoxy, methyl,

and an oxygen bonded to a silicon atom of another monomer.

Embodiment 10. The organosilica material of any one of the previousembodiments, wherein at least one independent unit of Formula (IV) ispresent, wherein each Z¹¹ represents a hydroxyl group, C₁-C₂ alkoxygroup or an oxygen bonded to a silicon atom of another comonomer; eachZ¹² and Z¹³ independently represent a hydroxyl group, a C₁-C₂ alkoxygroup, a C₁-C₂ alkyl group or an oxygen bonded to a silicon atom ofanother monomer; and each R² is selected from the group consisting aC₁-C₄ alkylene group, a C₂-C₄ alkenylene group, a C₂-C₄ alkynylene groupand a nitrogen-containing C₄-C₁₀ alkyl group.

Embodiment 11. The organosilica material of embodiment 10, wherein eachZ¹¹ independently represents a hydroxyl group, methoxy, ethoxy or anoxygen bonded to a silicon atom of another monomer; each Z¹² and Z¹³independently represent a hydroxyl group, methoxy, ethoxy, methyl or anoxygen bonded to a silicon atom of another monomer; and each R² isselected from the group consisting of —CH₂—, —CH₂CH₂—, —HC═CH—,

Embodiment 12. The organosilica material of any one of the previousembodiments, wherein at least one independent unit of Formula (V) ispresent, wherein M¹ is Al or B and each Z¹⁴ independently represents ahydrogen atom, a C₁-C₄ alkyl group or a bond to a silicon atom oranother monomer.

Embodiment 13. The organosilica material of any one of the previousembodiments, wherein at least one independent unit of Formula (VI) ispresent, wherein M² is Al or B; and each Z¹⁵ and each Z¹⁶ eachindependently represent a hydrogen atom, a C₁-C₄ alkyl group or a bondto a silicon atom of another monomer.

Embodiment 14. The organosilica material of any one of the previousembodiments, wherein the organosilica material is mesoporous and has anaverage pore diameter of about 2.0 nm to about 25.0 nm.

Embodiment 15. The organosilica material of any one of the previousembodiments, wherein the organosilica material has a total surface areaof about 200 m²/g to about 2500 m²/g.

Embodiment 16. The organosilica material of any one of the previousembodiments, wherein the organosilica material has a pore volume about0.2 cm³/g to about 3.0 cm³/g.

Embodiment 17. A method for preparing the organosilica material of anyone of the previous embodiments, the method comprising:

(a) providing an aqueous mixture that contains essentially no structuredirecting agent and/or porogen,

(b) adding at least one cyclic compound of Formula

into the aqueous mixture to form a solution, wherein each R³ isindependently a X¹OX²X³SiX⁴ group, wherein each X¹ represents a C₁-C₄alkyl group; each X² and X³ independently represent a C₁-C₄ alkyl group,or a C₁-C₄ alkoxy group; and each X⁴ represents a C₁-C₈ alkylene groupbonded to a nitrogen atom of the cyclic compound;

(c) aging the solution to produce a pre-product; and

(d) drying the pre-product to obtain an organosilica material which is apolymer comprising independent polyurea units of Formula (I).

Embodiment 18. The method of embodiment 17, wherein each X¹ represents aC₁-C₂ alkyl group; each X² and X³ independently represent a C₁-C₂ alkylgroup, or a C₁-C₂ alkoxy group; and each X⁴ represents a C₁-C₄ alkylenegroup bonded to a nitrogen atom of the cyclic compound.

Embodiment 19. The method of embodiment 17 or 18, wherein the at leastone compound of Formula (Ia) istris(3-trimethoxysilylpropyl)isocyanurate.

Embodiment 20. The method of any one of embodiments 17-19 furthercomprising adding to the aqueous mixture at least one compound selectedfrom the group consisting of

-   -   (i) a compound of Formula [X⁵OX⁶SiCH₂]₃ (IIa), wherein each X⁵        represents a C₁-C₄ alkyl group and each X⁶ represents a C₁-C₄        alkyl group or a C₁-C₄ alkoxy group;    -   (ii) a compound of Formula X⁷OX⁸X⁹X¹⁰Si (IIa), wherein each X⁷        represents a C₁-C₆ alkyl group; and X⁸, X⁹ and X¹⁰ are each        independently selected from the group consisting of a C₁-C₆        alkyl group, a C₁-C₆ alkoxy group, a nitrogen-containing C₁-C₁₀        alkyl group, a nitrogen-containing heteroaralkyl group, and a        nitrogen-containing optionally substituted heterocycloalkyl        group;    -   (iii)a compound of Formula X¹¹X¹²X¹³Si—R⁴—SiX¹¹X¹²X¹³ (IVa),        wherein each X¹¹ represents a C₁-C₄ alkoxy group; each X¹² and        X¹³ independently represent a C₁-C₄ alkoxy group or a C₁-C₄        alkyl group; and each R⁴ is selected from the group consisting a        C₁-C₈ alkylene group, a C₂-C₈ alkenylene group, a C₂-C₈        alkynylene group, a nitrogen-containing C₁-C₁₀ alkylene group,        an optionally substituted C₆-C₂₀ aralkyl and an optionally        substituted C₄-C₂₀ heterocycloalkyl group; and    -   (iv)a source of a trivalent metal oxide.

Embodiment 21. The method of embodiment 20, wherein the at least onecompound is a compound of Formula (IIa), wherein each X⁵ represents aC₁-C₂ alkyl group and each X⁶ represents a C₁-C₂ alkyl group or a C₁-C₂alkoxy group.

Embodiment 22. The method of embodiment 20 or 21, wherein the compoundof Formula (IIa) is 1,1,3,3,5,5-hexaethoxy-1,3,5-trisalacyclohexane or1,3,5-trimethyl-1,3,5-triethoxy-1,3,5-trisilacyclohexane.

Embodiment 23. The method of any one of embodiments 20-22, wherein theat least one compound is a compound of Formula (IIIa), wherein each X⁷is a C₁-C₂ alkyl group; and X⁸, X⁹ and X¹⁰ are each independentlyselected from the group consisting of a C₁-C₂ alkyl group, a C₁-C₂alkoxy group, a nitrogen-containing C₃-C₁₀ alkyl group, anitrogen-containing C₄-C₁₀ heteroaralkyl group, or a nitrogen-containingoptionally substituted C₄-C₁₀ heterocycloalkyl group.

Embodiment 24. The method of embodiment 23, wherein the compound ofFormula (IIIa) is selected from the group consisting of tetraethylorthosilicate or methyltriethoxysilane,(N,N-dimethylaminopropyl)trimethoxysilane,N-(2-aminoethyl)-3-aminopropyltriethoxysilane,4-methyl-1-(3-triethoxysilylpropyl)-piperazine,4-(2-(triethoxysily)ethyl)pyridine,1-(3-(triethoxysilyl)propyl)-4,5-dihydro-1H-imidazole, and(3-aminopropyl)triethoxysilane.

Embodiment 25. The method of any one of embodiments 20-24, wherein theat least one compound is a compound of Formula (IVa), wherein each X¹¹represents a C₁-C₂ alkoxy group; each X¹² and X¹³ independentlyrepresent a C₁-C₂ alkoxy group or a C₁-C₂ alkyl group; and each R⁴ isselected from the group consisting a C₁-C₄ alkylene group, a C₂-C₄alkenylene group, a C₂-C₄ alkynylene group, and a nitrogen-containingC₄-C₁₀ alkylene group.

Embodiment 26. The method of embodiment 25, wherein the compound ofFormula (IVa) is selected from the group consisting of1,2-bis(methyldiethoxysilyl)-ethane, bis(triethoxysilyl)methane,1,2-bis(triethoxysilyl)ethylene,N,N′-bis[(3-trimethoxysilyl)propyl]ethylenediamine,bis[(methyldiethoxysilyl)propyl]amine, andbis[(methyldimethoxysilyl)propyl]-N-methylamine.

Embodiment 27. The method of any one of embodiments 20-26, wherein thesource of a trivalent metal oxide is at least one of:

(i) a compound of Formula M³(OX¹⁴)₃ (Va), wherein M³ represents a Group13 metal and each X¹⁴ represents a C₁-C₆ alkyl; or

(ii) a compound of Formula (X¹⁵O)²M⁴-O—Si(OX¹⁶)₃ (VIa), wherein M⁴represents a Group 13 metal and each X¹⁵ and each X¹⁶ each independentlya C₁-C₆ alkyl group.

Embodiment 28. The method of embodiment 27, wherein the source oftrivalent metal is a compound of Formula (Va), wherein M³ is Al or B andeach X¹⁴ represents a C₁-C₄ alkyl group.

Embodiment 29. The method of embodiment 27, wherein the source oftrivalent metal is a compound of Formula (VIa), wherein M⁴ is Al or B;and each X¹⁵ and each X¹⁶ independently represent a C₁-C₄ alkyl.

Embodiment 30. The method of any one of embodiments 17-29, wherein theaqueous mixture comprises a base and has a pH from about 9 to about 14.

Embodiment 31. The method of embodiment 30, wherein the base is ammoniumhydroxide or a metal hydroxide.

Embodiment 32. The method of any one of embodiments 17-29, wherein theaqueous mixture comprises an acid and has a pH from about 0.3 to about4.5.

Embodiment 33. The method of embodiment 32, wherein the acid is aninorganic acid.

Embodiment 34. The method of embodiment 32 or 33, wherein the acid ishydrochloric acid.

Embodiment 35. The method of any one embodiments 17-34, wherein thesolution is aged in step (c) for up to 150 hours at a temperature ofabout 50° C. to about 200° C.

Embodiment 36. The method of any one embodiments 17-34, wherein the gelis dried at a temperature of about 70° C. to about 200° C.

Embodiment 37. An organosilica material obtainable by the method of anyone of embodiments 17-36.

Embodiment 38. A method for reducing impurities in a liquid hydrocarbonproduct comprising contacting the liquid hydrocarbon product with theorganosilica material of any one of embodiments 1-16 and 37.

Embodiment 39. The method of embodiment 38, wherein the liquidhydrocarbon product comprises diesel fuel, jet fuel, gasoline fueland/or lube base stock.

Embodiment 40. The method of embodiment 38 or 39, wherein the impuritiescomprise polar compounds and/or aromatic compounds.

Embodiment 41. The method of embodiment 40, wherein the polar compoundscomprise nitrogen-containing compounds and/or sulfur-containingcompounds.

Embodiment 42. The method of embodiment 40 or 41, wherein the aromaticcompounds comprise single ring aromatics, double ring aromatics, and/ormulti-ring aromatics.

Embodiment 43. The method of any one of embodiments 38-42, wherein theliquid hydrocarbon product comprises diesel fuel.

Embodiment 44. The method of embodiment 43, wherein at least about 0.1wt. %, or about 1.0 wt %, or about 5 wt. %, or about 10 wt. % of themulti-ring aromatics are removed from the diesel fuel.

Embodiment 45. The method of embodiment 43 or 44, wherein the dieselfuel is contacted with the organosilica material at a temperature ofabout 18° C. to about 200° C. and/or a pressure of about 5 psi to about100 psi.

Embodiment 46. The method of any one of embodiments 43-45, wherein thediesel fuel comprises less than or equal to about 50 ppm sulfur.

Embodiment 47. The method of any one of embodiments 43-46, wherein thediesel fuel has a color level of less than or equal to 3.0 as measuredaccording to D6045 ASTM following contact with the organosilicamaterial.

Embodiment 48. The method of any one of embodiments 38-47, wherein theorganosilica material has selectivity of at least 1.3 for multi-ringaromatics compared to total ring aromatics.

Embodiment 49. The method of any one of embodiments 38-48, wherein theorganosilica material is packed into a column and the liquid hydrocarbonproduct is contacted therein.

Embodiment 50. The method of any one of embodiments 43-49, wherein thediesel fuel is contacted with the organosilica material followinghydrotreatment of the diesel fuel.

Embodiment 51. A method for improving color in a diesel fuel productcomprising contacting the diesel fuel product with the organosilicamaterial of any one of embodiments 1-16 and 37 resulting in an improvedcolor diesel fuel product.

Embodiment 52. The method of embodiment 51, wherein the diesel fuelproduct is contacted with the organosilica material at a temperature ofabout 18° C. to about 200° C. and/or a pressure of about 5 psi to about100 psi.

Embodiment 53. The method of embodiment 51 or 52, wherein the dieselfuel product is contacted with the organosilica material followinghydrotreatment of the diesel fuel.

Embodiment 54. The method of any one of embodiments 51-53, wherein thediesel fuel product has a color level of at least about 5.0 as measuredaccording to D6045 ASTM prior to contact with the organosilica material.

Embodiment 55. The method of any one of embodiments 51-54, wherein theimproved color diesel fuel product has a color level of less than orequal to about 3.0 as measured according to D6045 ASTM.

Embodiment 56. The method of any one of embodiments 51-55, wherein theorganosilica material is packed into a column.

EXAMPLES General Methods Small Angle X-ray Diffraction Analysis

X-ray powder diffraction (XRD) patterns were collected on a PANalyticalX′pert diffractometer equipped with an accessory for low anglemeasurements. XRD analyses were recorded using the Cu Ka (=1.5405980Å)line in the 2θ range from 0.5 to 10° with a step size of 0.0167° and acounting time of 1.2 s.

Solid-State (SS) NMR Measurements

The ²⁹Si MAS NMR spectra were recorded on a Varian InfinityPlus-400spectrometer (operating at 9.4 T) and Varian InfinityPlus-500 (operatingat 11.74 T), corresponding to ²⁹Si Larmor frequencies of 79.4 MHz and99.2 MHz, respectively, with a 7.5 mm MAS probe heads using 5 kHzspinning, 4.0 μs 90° pulses, and at least 60 s recycle delay, withproton decoupling during data acquisition. The ²⁹Si chemical shifts arereferenced with respect to an external tetramethyl silane (δ_(Si)=0.0ppm). The ¹³C CPMAS NMR spectra were recorded on a VarianInfinityPlus-500 spectrometer corresponding to ¹³C Larmor frequency of125 MHz, with 1.6 mm MAS probe head using 40 kHz spinning, ¹H-¹³Ccross-polarization (CP) contact time of at least 1 ms, a recycle delayof at least 1 s, with proton decoupling during data acquisition. The ¹³Cchemical shifts are referenced with respect to an external tetramethylsilane (δ_(C)=0.0 ppm). The ²⁷Al MAS NMR spectra were recorded on aVarian InfinityPlus-500 corresponding to ²⁷Al Larmor frequency of 130.1MHz using a 4 mm MAS probe head using 12 kHz spinning, with a π/12radian pulse length, with proton decoupling during data acquisition, anda recycle delay of 0.3 s. The chemical shifts are referenced withrespect to an external solution of Al(H₂O)₆ ³⁺(δ_(A1)=0.0 ppm). All NMRspectra were recorded at room temperature using air for spinning.

Thermal Gravimetric Analysis (TGA)

Thermal stability results were recorded on Q5000 TGA. Ramp rate was 5°C./min, temperature range was from 25° C. to 800° C. All the sampleswere tested in both air and nitrogen.

CO₂ Adsorption

The work was done with a Quantchrom autosorb iQ2. All the samples werepre-treated at 120° C. in vacuum for 3 hours before collecting the CO₂isotherm at different temperatures.

Nitrogen Porosimetry

The nitrogen adsorption/desorption analyses was performed with differentinstruments, e.g. TriStar 3000, TriStar II 3020 and Autosorb-1. All thesamples were pre-treated at 120° C. in vacuum for 4 hours beforecollecting the N₂ isotherm. The analysis program calculated theexperimental data and report BET surface area, microporous surface area(S), total pore volume, pore volume for micropores, average porediameter (or radius), etc.

Example 1 Organosilica Material Syntheses using Formula (Ia), Formula(IIa) and/or Formula (IIIa) 1A. Synthesis usingtris(3-trimethoxysilylpropyl)isocyanurate.

A solution with 6.23 g 30 wt. % NH₄OH and 7.92 g DI water (53 mmolNH₄OH; 682 mmol H₂O) was made. To the solution 1.53 g oftris(3-trimethoxysilylpropyl)isocyanurate (2.5 mmol) was added toproduce a solution having the molar composition:

2.5 tris(3-trimethoxysilylpropyl)isocyanurate : 53 NH₄OH: 682 H₂O whichwas stirred at 22-25° C. for 1 day. The solution was transferred to anoven and kept at 70-75° C. for 1 day to produce a gel. The gel was driedin a vacuum at 120° C. overnight (16-24 hours) and Sample 1 wasobtained. No surface directing agent or porogen were used.

XRD Analysis

XRD was performed on Sample 1. The XRD pattern of Sample 1 is shown inFIG. 4.

Nitrogen Adsorption/Desorption Analysis

Nitrogen adsorption/desorption analysis was performed on Sample 1, andthe results are provided in Table 1 below.

1B. Synthesis using tris(3-trimethoxysilylpropyl)isocyanurate andtetraethylorthosilicate(TEOS) ((EtO₄)Si).

A solution with 6.23 g 30 wt. % NH₄OH and 7.92 g DI water (53 mmolNH₄OH; 682 mmol H₂O) was made. To the solution 0.61 g oftris(3-trimethoxysilylpropyl)isocyanurate (1 mmol) and 0.312 g TEOS (1.5mmol) was added to produce a solution having the molar composition:

1 tris(3-trimethoxysilylpropyl)isocyanurate: 1.5 TEOS : 53 NH₄OH: 682 H₂O which was stirred at 22-25° C. for 1 day. The solution was transferredto an oven and kept at 70-75° C. for 1 day to produce a gel. The gel wasdried in a vacuum at 120° C. overnight (16-24 hours) and Sample 2 wasobtained. No surface directing agent or porogen were used.

XRD Analysis

XRD was performed on Sample 2. The XRD pattern of Sample 2 is shown inFIG. 5.

Nitrogen Adsorption/Desorption Analysis

Nitrogen adsorption/desorption analysis was performed on Sample 2, andthe results are provided in Table 1 below.

1C. Synthesis using tris(3-trimethoxysilylpropyl)isocyanurate and[(EtO)₂SiCH₂]₃,

A solution with 31.15 g 30 wt. % NH₄OH and 39.9 g DI water (265 mmolNH₄OH; 3.410 mol H₂O) was made. To the solution 12.2 g oftris(3-trimethoxysilylpropyl)isocyanurate (20 mmol) and 12 g of[(EtO)₂SiCH₂]₃ (30 mmol) was added to produce a solution having themolar composition: 4 tris(3-trimethoxysilylpropyl)isocyanurate: 6[(EtO)₂SiCH₂]₃: 53 NH₄OH: 682 H₂O which was stirred at 22-25° C. for 1day. The solution was transferred to an oven and kept at 70-75° C. for 1day to produce a gel. The gel was dried in a vacuum at 120° C. overnight(16-24 hours) and Sample 3 was obtained. No surface directing agent orporogen were used.

Nitrogen Adsorption/Desorption Analysis

Nitrogen adsorption/desorption analysis was performed on Sample 3, andthe results are provided in Table 1 below.

TABLE 1 BET S (m²/g, Pore Pore Volume Material (m²/g) micro) diameter(nm) (cc/g) Sample 1 659 220 2.79 0.459 Sample 2 733 0 3.84 0.64 Sample3 769 0 3.88 0.734

Example 2 Batch Adsorption Experiment on Discolored Diesel Product

Experiments were done on a Perkin Elmer Lambda 850 UV-Visspectrophotometer with Scantraq software by FTG. Samples were analyzedat room temp (˜15-25 C) in a ˜1 mm flow cell. If necessary, samples maybe combined with cyclohexane in solution.

Sample 3 was tested in batch adsorption experiments on a discoloreddiesel product which was generated by high-temperature hydroteating ofan on-spec diesel product. The feed color was measured according to ASTMD6045. The properties of the neat feed are shown below in Table 2.

TABLE 2 High-temperature Hydrotreated Diesel Property Product ColorLevel (D6045 ASTM L5.0 Method) Sulfur (ppm) 2.8 Total Nitrogen (ppm) 0.2PARAFFINS (wt. %) 5.61 1-RING NAPHTHENES (wt. %) 12.18 2+ RINGNAPHTHENES (wt. %) 38.22 1 RING AROMATICS (wt. %) 29.89 2 RING AROMATICS(wt. %) 8.41 3+ RINGS AROMATICS (wt. %) 5.69 TOTAL NAPHTHENES (wt. %)50.41 TOTAL AROMATICS (wt. %) 43.98

The reduction of multi-ring aromatic compounds in the diesel feedtreated with Sample 3 based on UV-Vis adsorption is shown below in Table3. Aromatic content in a diesel sample can be determined by anyconvenient method. ASTM D2008 provides one example of a method ofcorrelating UV-Vis data with a weight of aromatics in a sample. UVabsorbance at 226 nm has previously been used to characterize the totalaromatics content in a product, see U.S. Pat. No. 6,569,312. UVabsorbance at 325 nm indicates the multi-ring aromatic content. Theratio of absorptivity at 325 nm to absorptivity at 226 nm shows theselectivity of multi-ring aromatic removal. UV-Vis adsorption spectrafor the feed and Sample 3 is shown in FIG. 1. As shown in FIG. 1, colorimprovement in the diesel feed is evidenced by the reduction of visiblerange absorption peak intensity at 400-600-nm wavelengths. Additionally,FIG. 2 provides a photograph of the feed before and after adsorption. Asshown in FIG. 2, there was color improvement for the diesel feed treatedwith Sample 3 (lighter color) versus untreated diesel feed (darkercolor).

TABLE 3 Ratio of Absorptivity Absorptivity absorptivity @ 226 nm @ 325nm @325 nm/ % % Absorptivity l/g-cm Reduction l/g-cm Reduction @ 226 nmFeed 46.675 — 0.3899 — Sample 3 43.847 6.1% 0.36 7.7 1.3

What is claimed is:
 1. An organosilica material, which is a polymer ofat least one independent cyclic polyurea monomer of Formula

wherein each R¹ independently is a Z¹OZ²Z³SiZ⁴ group, wherein each Z¹represents a hydrogen atom, a C₁-C₄ alkyl group, or a bond to a siliconatom of another monomer unit; each Z² and Z³ independently represent ahydroxyl group, a C₁-C₄ alkyl group, a C₁-C₄ alkoxy group or an oxygenatom bonded to a silicon atom of another monomer unit; and each Z⁴represents a C₁-C₈ alkylene group bonded to a nitrogen atom of thecyclic polyurea; and optionally at least one other monomer selected fromthe group consisting of: (vii) an independent unit of Formula[Z⁵OZ⁶SiCH₂]₃ (II), wherein each Z⁵ represents a hydrogen atom, a C₁-C₄alkyl or a bond to a silicon atom of another monomer, and each Z⁶represents a hydroxyl group, a C₁-C₄ alkyl group, a C₁-C₄ alkoxy group,or an oxygen atom bonded to a silicon atom of another monomer; (viii) anindependent unit of Formula Z⁷OZ⁸Z⁹Z¹⁰Si (III), wherein each Z⁷represents a hydrogen atom, a C₁-C₄ alkyl group or a bond to a siliconatom of another monomer; and Z⁸, Z⁹ and Z¹⁰ are each independentlyselected from the group consisting of a hydroxyl group, a C₁-C₄ alkylgroup, a C₁-C₄ alkoxy group, a nitrogen-containing C₁-C₁₀ alkyl group, anitrogen-containing heteroaralkyl group, and a nitrogen-containingoptionally substituted heterocycloalkyl group, and an oxygen atom bondedto a silicon atom of another monomer; (ix) an independent unit ofFormula Z¹¹Z¹²Z¹³Si—R²—SiZ¹¹Z¹²Z¹³ (IV), wherein each Z¹¹ independentlyrepresents a hydroxyl group, a C₁-C₄ alkoxy group or an oxygen bonded toa silicon atom of another comonomer; each Z¹² and Z¹³ independentlyrepresent a hydroxyl group, a C₁-C₄ alkoxy group, a C₁-C₄ alkyl group oran oxygen bonded to a silicon atom of another monomer; and R² a C₁-C₈alkylene group, a C₂-C₈ alkenylene group, a C₂-C₈ alkynylene group, anitrogen-containing C₂-C₁₀ alkylene group, an optionally substitutedC₆-C₂₀ aralkyl and an optionally substituted C₄-C₂₀ heterocycloalkylgroup; (x) an independent unit of Formula M¹(OZ¹⁴)₃ (V), wherein M¹represents a Group 13 metal and each Z¹⁴ independently represents ahydrogen atom, a C₁-C₆ alkyl or a bond to a silicon atom of anothermonomer; (xi) an independent unit of Formula (Z ¹⁵O)₂M²-O—Si(OZ¹⁶)₃(VI), wherein M² represents a Group 13 metal and each Z¹⁵ and each Z¹⁶independently represent a hydrogen atom, a C₁-C₆ alkyl group or a bondto a silicon atom of another monomer; and (xii) a combination thereof.2. The organosilica material of claim 1, wherein each Z¹ represents ahydrogen atom, a C₁-C₂ alkyl group or a bond to a silicon atom ofanother monomer unit; each Z² and Z³ independently represent a hydroxylgroup, a C₁-C₂ alkyl group, a C₁-C₂ alkoxy group or an oxygen atombonded to a silicon atom of another monomer unit and each Z⁴ representsa C₁-C₄ alkylene group bonded to a nitrogen atom of the cyclic polyurea.3. The organosilica material of claim 1, wherein each Z¹ represents ahydrogen atom, methyl or a bond to a silicon atom of another monomerunit; each Z² and Z³ independently represent a hydroxyl group, methoxyor an oxygen atom bonded to a silicon atom of another monomer unit andeach Z⁴ represents —CH₂CH₂CH₂— bonded to a nitrogen atom of the cyclicpolyurea.
 4. The organosilica material of claim 1, wherein at least oneindependent unit of Formula (II) is present, wherein each Z⁵ representsa hydrogen atom, a C₁-C₂ alkyl or a bond to a silicon atom of anothercomonomer, and each Z⁶ represents a hydroxyl group, a C₁-C₂ alkyl group,a C₁-C₂ alkoxy group or an oxygen bonded to a silicon atom of anothermonomer.
 5. The organosilica material of claim 4, wherein each Z⁵represent a hydrogen atom, ethyl or a bond to a silicon atom of anothermonomer and each Z⁶ represents a hydroxyl group, methyl, ethoxy or anoxygen bonded to a silicon atom of another monomer.
 6. The organosilicamaterial of claim 4, wherein each Z⁵ represent a hydrogen atom, ethyl ora bond to a silicon atom of another monomer and each Z⁶ represents ahydroxyl group, ethoxy or an oxygen bonded to a silicon atom of anothermonomer.
 7. The organosilica material of claim 4, wherein each Z⁵represent a hydrogen atom, ethyl or a bond to a silicon atom of anothermonomer and each Z⁶ represents methyl.
 8. The organosilica material ofclaim 1, wherein at least one independent unit of Formula (III) ispresent, wherein each Z⁷ represents a hydrogen atom, a C₁-C₂ alkyl groupor a bond to a silicon atom of another comonomer; and Z⁸, Z⁹ and Z¹⁰ areeach independently selected from the group consisting of a hydroxylgroup, a C₁-C₂ alkyl group, C₁-C₂ alkoxy group, a nitrogen-containingC₃-C₁₀ alkyl group, a nitrogen-containing C₄-C₁₀ heteroaralkyl group, ora nitrogen-containing optionally substituted C₄-C₁₀ heterocycloalkylgroup, and an oxygen atom bonded to a silicon atom of another monomer.9. The organosilica material of claim 8, wherein each Z⁷ represents ahydrogen atom, methyl, ethyl, or a bond to a silicon atom of anothercomonomer; and Z⁸, Z⁹ and Z¹⁰ are each independently selected from thegroup consisting of a hydroxyl group, methoxy, ethoxy, methyl,

and an oxygen bonded to a silicon atom of another monomer.
 10. Theorganosilica material of claim 1, wherein at least one independent unitof Formula (IV) is present, wherein each Z¹¹ represents a hydroxylgroup, C₁-C₂ alkoxy group or an oxygen bonded to a silicon atom ofanother comonomer; each Z¹² and Z¹³ independently represent a hydroxylgroup, a C₁-C₂ alkoxy group, a C₁-C₂ alkyl group or an oxygen bonded toa silicon atom of another monomer; and each R² is selected from thegroup consisting a C₁-C₄ alkylene group, a C₂-C₄ alkenylene group, aC₂-C₄ alkynylene group and a nitrogen-containing C₄-C₁₀ alkyl group. 11.The organosilica material of claim 10, wherein each independentlyrepresents a hydroxyl group, methoxy, ethoxy or an oxygen bonded to asilicon atom of another monomer; each Z¹² and Z¹³ independentlyrepresent a hydroxyl group, methoxy, ethoxy, methyl or an oxygen bondedto a silicon atom of another monomer; and each R² is selected from thegroup consisting of —CH₂—, —CH₂CH₂—, —HC═CH—,


12. The organosilica material of claim 1, wherein at least oneindependent unit of Formula (V) is present, wherein M¹ is Al or B andeach Z¹⁴ independently represents a hydrogen atom, a C₁-C₄ alkyl groupor a bond to a silicon atom or another monomer.
 13. The organosilicamaterial of claim 1, wherein at least one independent unit of Formula(VI) is present, wherein M² is Al or B; and each Z¹⁵ and each Z¹⁶independently represent a hydrogen atom, a C₁-C₄ alkyl group or a bondto a silicon atom of another monomer.
 14. The organosilica material ofclaim 1, wherein the organosilica material is mesoporous and has anaverage pore diameter of about 2.0 nm to about 25.0 nm.
 15. Theorganosilica material of claim 1, wherein the organosilica material hasa total surface area of about 200 m²/g to about 2500 m²/g.
 16. Theorganosilica material of claim 1, wherein the organosilica material hasa pore volume about 0.2 cm³/g to about 3.0 cm³/g.
 17. A method forpreparing the organosilica material of claim 1, the method comprising:(a) providing an aqueous mixture that contains essentially no structuredirecting agent and/or porogen, (b) adding at least one cyclic compoundof Formula

into the aqueous mixture to form a solution, wherein each R³ isindependently a X¹OX²X³SiX⁴ group, wherein each X¹ represents a C₁-C₄alkyl group; each X² and X³ independently represent a C₁-C₄ alkyl group,or a C₁-C₄ alkoxy group; and each X⁴ represents a C₁-C₈ alkylene groupbonded to a nitrogen atom of the cyclic compound; (c) aging the solutionto produce a pre-product; and (d) drying the pre-product to obtain anorganosilica material which is a polymer comprising independent polyureaunits of Formula (I).
 18. The method of claim 17, wherein each X¹represents a C₁-C₂ alkyl group; each X² and X³ independently represent aC₁-C₂ alkyl group, or a C₁-C₂ alkoxy group; and each X⁴ represents aC₁-C₄ alkylene group bonded to a nitrogen atom of the cyclic compound.19. The method of claim 17, wherein the at least one compound of Formula(Ia) is tris(3-trimethoxysilylpropyl)isocyanurate.
 20. The method ofclaim 17 further comprising adding to the aqueous mixture at least onecompound selected from the group consisting of (i) a compound of Formula[X⁵OX⁶SiCH₂]₃ (IIa), wherein each X⁵ represents a C₁-C₄ alkyl group andeach X⁶ represents a C₁-C₄ alkyl group or a C₁-C₄ alkoxy group; (ii) acompound of Formula X⁷OX⁸X⁹X¹⁰Si (IIIa), wherein each X⁷ represents aC₁-C₆ alkyl group; and X⁸, X⁹ and X¹⁰ are each independently selectedfrom the group consisting of a C₁-C₆ alkyl group, a C₁-C₆ alkoxy group,a nitrogen-containing C₁-C₁₀ alkyl group, a nitrogen-containingheteroaralkyl group, and a nitrogen-containing optionally substitutedheterocycloalkyl group; (iii) a compound of FormulaX¹¹X¹²X¹³Si—R⁴—SiX¹¹X¹²X¹³ (IVa), wherein each X¹¹ representsa C₁-C₄alkoxy group; each X¹² and X¹³ independently represent a C₁-C₄ alkoxygroup or a C₁-C₄ alkyl group; and each R⁴ is selected from the groupconsisting a C₁-C₈ alkylene group, a C₂-C₈ alkenylene group, a C₂-C₈alkynylene group, a nitrogen-containing C₁-C₁₀ alkylene group, anoptionally substituted C₆-C₂₀ aralkyl and an optionally substitutedC₄-C₂₀ heterocycloalkyl group; and (iv) a source of a trivalent metaloxide.
 21. The method of claim 20, wherein the at least one compound isa compound of Formula (IIa), wherein each X⁵ represents a C₁-C₂ alkylgroup and each X⁶ represents a C₁-C₂ alkyl group or a C₁-C₂ alkoxygroup.
 22. The method of claim 20, wherein the compound of Formula (IIa)is 1,1,3,3,5,5-hexaethoxy-1,3,5-trisalacyclohexane or1,3,5-trimethyl-1,3,5-triethoxy-1,3,5-trisilacyclohexane.
 23. The methodof claim 20, wherein the at least one compound is a compound of Formula(IIIa), wherein each X⁷ is a C₁-C₂ alkyl group; and X⁸, X⁹ and X¹⁰ areeach independently selected from the group consisting of a C₁-C₂ alkylgroup, a C₁-C₂ alkoxy group, a nitrogen-containing C₃-C₁₀ alkyl group, anitrogen-containing C₄-C₁₀ heteroaralkyl group, or a nitrogen-containingoptionally substituted C₄-C₁₀ heterocycloalkyl group.
 24. The method ofclaim 23, wherein the compound of Formula (IIIa) is selected from thegroup consisting of tetraethyl orthosilicate or methyltriethoxysilane,(N,N-dimethylaminopropyl)trimethoxysilane,N-(2-aminoethyl)-3-aminopropyltriethoxysilane,4-methyl-1-(3-triethoxysilylpropyl)-piperazine,4-(2-(triethoxysily)ethyl)pyridine, 1-(3-(triethoxysilyl)propyl)-4,5-dihydro-1H-imidazole, and (3-aminopropyl)triethoxysilane.
 25. Themethod of claim 20, wherein the at least one compound is a compound ofFormula (IVa), wherein each X¹¹ represents a C₁-C₂ alkoxy group; eachX¹² and X¹³ independently represent a C₁-C₂ alkoxy group or a C₁-C₂alkyl group; and each R⁴ is selected from the group consisting a C₁-C₄alkylene group, a C₂-C₄ alkenylene group, a C₂-C₄ alkynylene group, anda nitrogen-containing C₄-C₁₀ alkylene group.
 26. The method of claim 25,wherein the compound of Formula (IVa) is selected from the groupconsisting of 1,2-bis(methyldiethoxysilyl)ethane,bis(triethoxysilyl)methane, 1,2-bis(triethoxysilyl)ethylene,N,N′-bis[(3-trimethoxysilyl)propyl]ethylenediamine,bis[(methyldiethoxysilyl)propyl]amine, andbis[(methyldimethoxysilyl)propyl]-N-methylamine.
 27. The method of claim20, wherein the source of a trivalent metal oxide is at least one of:(i) a compound of Formula M³(OX¹⁴)₃ (Va), wherein M³ represents a Group13 metal and each X¹⁴ represents a C₁-C₆ alkyl; or (ii)a compound ofFormula (X¹⁵O)²M⁴-O—Si(OX¹⁶)₃ (VIa), wherein M⁴ represents a Group 13metal and each X¹⁵ and each X¹⁶ independently a C₁-C₆ alkyl group. 28.The method of claim 27, wherein the source of trivalent metal is acompound of formula (Va), wherein M³ is Al or B and each X¹⁴ representsa C₁-C₄ alkyl group.
 29. The method of claim 27, wherein the source oftrivalent metal is a compound of formula (VIa), wherein M⁴ is Al or B;and each X¹⁵ and each X¹⁶ independently represent a C₁-C₄ alkyl.
 30. Themethod of claim 17, wherein the aqueous mixture comprises a base and hasa pH from about 9 to about
 14. 31. The method of claim 30, wherein thebase is ammonium hydroxide or a metal hydroxide.
 32. The method of claim17, wherein the aqueous mixture comprises an acid and has a pH fromabout 0.3 to about 4.5.
 33. The method of claim 32, wherein the acid isan inorganic acid.
 34. The method of claim 33, wherein the acid ishydrochloric acid.
 35. The method of claim 17, wherein the solution isaged in step (c) for up to 150 hours at a temperature of about 50° C. toabout 200° C.
 36. The method of claim 17, wherein the pre-product isdried at a temperature of about 70° C. to about 200° C.
 37. Anorganosilica material obtainable by the method of claim
 17. 38. A methodfor reducing impurities in a liquid hydrocarbon product comprisingcontacting the liquid hydrocarbon product with the organosilica materialof claim
 1. 39. The method of claim 38, wherein the liquid hydrocarbonproduct comprises diesel fuel, jet fuel, gasoline fuel and/or lube basestock.
 40. The method of claim 38, wherein the impurities comprise polarcompounds and/or aromatic compounds.
 41. The method of claim 40, whereinthe polar compounds comprise nitrogen-containing compounds and/orsulfur-containing compounds.
 42. The method of claim 40, wherein thearomatic compounds comprise single ring aromatics, double ringaromatics, and/or multi-ring aromatics.
 43. The method of claim 38,wherein the liquid hydrocarbon product comprises diesel fuel.
 44. Themethod of claim 43, wherein at least about 0.1 wt. % of the multi-ringaromatics are removed from the diesel fuel.
 45. The method of claim 43,wherein the diesel fuel is contacted with the organosilica material at atemperature of about 18° C. to about 200° C. and/or a pressure of about5 psi to about 100 psi.
 46. The method of claim 43, wherein the dieselfuel comprises less than or equal to about 50 ppm sulfur.
 47. The methodof claim 43, wherein the diesel fuel has a color level of less than orequal to 3.0 as measured according to D6045 ASTM following contact withthe organosilica material.
 48. The method of claim 38, wherein theorganosilica material has selectivity of at least 1.3 for multi-ringaromatics compared to total ring aromatics.
 49. The method of claim 38,wherein the organosilica material is packed into a column and the liquidhydrocarbon product is contacted therein.
 50. The method of claim 43,wherein the diesel fuel is contacted with the organosilica materialfollowing hydrotreatment of the diesel fuel.
 51. A method for improvingcolor in a diesel fuel product comprising contacting the diesel fuelproduct with the organosilica material of claim 1 resulting in animproved color diesel fuel product.
 52. The method of claim 51, whereinthe diesel fuel product is contacted with the organosilica material at atemperature of about 18° C. to about 80° C. and/or a pressure of about 5psi to about 16 psi.
 53. The method of claim 51, wherein the diesel fuelproduct is contacted with the organosilica material followinghydrotreatment of the diesel fuel.
 54. The method of claim 51, whereinthe diesel fuel product has a color level of at least about 5.0 asmeasured according to D6045 ASTM prior to contact with the organosilicamaterial.
 55. The method of claim 51, wherein the improved color dieselfuel product has a color level of less than or equal to about 3.0 asmeasured according to D6045 ASTM.
 56. The method of claim 51, whereinthe organosilica material is packed into a column.